EP3235854A1 - Polyarylene ether sulfone polymers for membrane applications - Google Patents
Polyarylene ether sulfone polymers for membrane applications Download PDFInfo
- Publication number
- EP3235854A1 EP3235854A1 EP17169719.6A EP17169719A EP3235854A1 EP 3235854 A1 EP3235854 A1 EP 3235854A1 EP 17169719 A EP17169719 A EP 17169719A EP 3235854 A1 EP3235854 A1 EP 3235854A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- weight
- reaction mixture
- polyarylene ether
- ether sulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 114
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 96
- -1 ether sulfone Chemical class 0.000 title claims abstract description 94
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 94
- 239000012528 membrane Substances 0.000 title claims abstract description 58
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 73
- 239000011541 reaction mixture Substances 0.000 claims abstract description 64
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 35
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 91
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 49
- 239000002798 polar solvent Substances 0.000 claims description 33
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000012510 hollow fiber Substances 0.000 claims description 17
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005345 coagulation Methods 0.000 claims description 15
- 230000015271 coagulation Effects 0.000 claims description 15
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 12
- 238000000502 dialysis Methods 0.000 claims description 11
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 210000004379 membrane Anatomy 0.000 description 43
- 239000000243 solution Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 31
- 235000011181 potassium carbonates Nutrition 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 230000035484 reaction time Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 12
- 229920002492 poly(sulfone) Polymers 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 235000017550 sodium carbonate Nutrition 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 238000013459 approach Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229940050176 methyl chloride Drugs 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000002166 wet spinning Methods 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920006393 polyether sulfone Polymers 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229920006258 high performance thermoplastic Polymers 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- WEKKRIKVUVKGKV-UHFFFAOYSA-N 4-(4-hydroxyphenyl)phenol;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WEKKRIKVUVKGKV-UHFFFAOYSA-N 0.000 description 1
- QYFPAMPUSZKIDM-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3-dimethylcyclopentyl]phenol Chemical compound C1C(C)(C)CCC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 QYFPAMPUSZKIDM-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- CEXKLNUJKWPGSK-UHFFFAOYSA-L dipotassium 4-(4-hydroxyphenyl)phenol carbonate Chemical compound C([O-])([O-])=O.[K+].OC1=CC=C(C=C1)C1=CC=C(C=C1)O.[K+] CEXKLNUJKWPGSK-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical class C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4056—(I) or (II) containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
- B29K2081/06—PSU, i.e. polysulfones; PES, i.e. polyethersulfones or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/755—Membranes, diaphragms
Definitions
- the present invention relates to a process for preparing a polyarylene ether sulfone polymer by reacting a reaction mixture (R G ) containing a dihalogen component (A1), a dihydroxy component (B1) and potassium carbonate (C1) having a volume-average particle size of ⁇ 25 microns.
- the present invention relates to the polyarylene ether sulfone polymers obtainable by the process and to products obtainable from the polyarylene ether sulfone polymer and to membranes made from the polyarylene ether sulfone polymer.
- Polyarylene ether sulfone polymers belong to the group of high-performance thermoplastics and are distinguished by high heat resistance, good mechanical properties and inherent flame retardancy (US Pat. EM Koch, H.-M. Walter, Kunststoffe 80 (1990) 1146 ; E. Döring, Kunststoffe 80, (1990) 1149 . N. Inchaurondo-Nehm, Kunststoffe 98, (2008) 190 ). Due to their good biocompatibility, polyarylene ethers are also used as material for the preparation of dialysis membranes ( NA Hoenich, KP Katapodis, Biomaterials 23 (2002) 3853 ).
- the preparation of the polyarylene ether sulfone polymers can take place, inter alia, either via the hydroxide method in which a salt is first prepared from the dihydroxy component and the hydroxide, or via the so-called carbonate method.
- General information on the preparation of the polyarylene ether sulfone polymers by the hydroxide method can be found, inter alia RN Johnson et.al., J. Polym. Sci. A-1 5 (1967) 2375 while at JE McGrath et al., Polymer 25 (1984) 1827 , the carbonate method is described.
- thermoplastics such as polyarylene ether sulfone polymers
- polycondensation reactions which are usually carried out at high reaction temperature in dipolar aprotic solvents such as DMF, DMAc, sulfolane, DMSO and NMP.
- EP 0 412 499 a process for the preparation of polyarylene ether sulfone polymers is described.
- Dihalogenkomponente come in the process according to EP 0 412 499 for example, 4,4'-dichlorodiphenylsulfone or 4,4'-difluorodiphenylsulfone used.
- dihydroxy component are in the EP 0 412 499 bisphenol A, 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxybenzophenone, among others, are described.
- the polycondensation according to EP 0 412 499 takes place in the presence of sodium carbonate or sodium bicarbonate (sodium bicarbonate).
- the sodium carbonate used is finely ground and has particle sizes (D 90%) of ⁇ 20 microns.
- D 90% particle sizes
- the polydispersity of the polyarylene ether sulfone polymers obtainable by this process is relatively high.
- the reaction time for the preparation of the polyarylene ether sulfone polymers is too long for an economical process.
- the dihydroxy component used is at least 75 mol%, preferably at least 90 mol%, of 4,4'-dihydroxybiphenyl. That in the WO 01/66620 described polybiphenyl ether sulfone polymer thus has at least 75 mol%, preferably at least 90 mol% of 4,4'-biphenylene units, based on the dihydroxy compound used.
- a dihalogen component for example, 4,4'-dichlorodiphenyl sulfone is described.
- polycondensation is carried out in the presence of a metal carbonate, preferably potassium carbonate, whose particle size is in the range of 10 to 30 microns.
- a metal carbonate preferably potassium carbonate
- polybiphenylene ether sulfone polymers having a low intrinsic color are obtained.
- the according to the method according to WO 01/66620 available Polybiphenylethersulfon polymers have, especially for membrane applications, insufficient mechanical properties.
- the polybiphenyl ether sulfone polymers are characterized by a relatively high polydispersity.
- polydispersity In the process described in the prior art for the preparation of polyarylene ether sulfone polymers usually very broad molecular weight distributions are obtained. A measure of the molecular weight distribution is the polydispersity (Q).
- the polydispersity (Q) is defined as the quotient of the weight average molecular weight (Mw) and number average molecular weight (M n ). Polydispersities (Q) of significantly greater than 3.5 are usually obtained in the processes described in the prior art.
- Polyarylene ether sulfone polymers having polydispersities (Q) of> 4 are of limited use, in particular, for the production of membranes.
- the aim of the invention is moreover to provide a process in which cyclic oligomers need not be separated.
- the object of the invention is achieved by the method according to the invention.
- reaction mixture (R G ) which contains the above-described components (A1), (B1), (C) and optionally (D).
- the components (A1) and (B1) enter into a polycondensation reaction.
- Component (D) serves as a solvent.
- Component (C) serves as a base to deprotonate component (B1) during the condensation reaction.
- reaction mixture (R G ) is understood to mean the mixture which is used in the process according to the invention for the preparation of the polyarylene ether sulfone polymer.
- all data relating to the reaction mixture (R G ) thus refer to the mixture which is present before the polycondensation.
- the polycondensation takes place, wherein the reaction mixture (R G ) by polycondensation of the components (A1) and (B1) to the target product, the polyarylene ether sulfone polymer, is reacted.
- the mixture obtained after the polycondensation, which contains the target product, the polyarylene ether sulfone polymer is also referred to as a product mixture (P G ).
- reaction mixture R G
- the individual components can be in an upstream Step mixed and then reacted. It is also possible to feed the individual components to a reactor in which they are mixed and subsequently reacted.
- the individual components of the reaction mixture (R G ) are generally reacted together.
- the reaction is preferably carried out in one stage. That is, the deprotonation of the component (B1) and the condensation reaction between the components (A1) and (B1) takes place in a single reaction stage, without isolated intermediates, such as the deprotonated species of component (B1).
- the reaction mixture (R G ) contains at least one dihalogen compound.
- at least one dihalogen compound is meant in the present case exactly one dihalogen compound and mixtures of two or more dihalogen compounds.
- the component (A1) can thus be both a single dihalogen compound and a mixture of two or more dihalogen compounds.
- component (A1) contains at least 50% by weight of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, based on the total weight of component (A1) in the formula Reaction mixture (R G ).
- the percentages by weight with respect to component (A1) also refer to the sum of the 4,4'-dichlorodiphenylsulfone used and the 4,4'-difluorodiphenylsulfone used.
- 4,4'-dichlorodiphenylsulfone is preferred.
- the 4,4'-dichlorodiphenyl sulfone and the 4,4'-difluorodiphenyl sulfone can be used as a pure substance or as a technical product, which can be up to 2 wt .-%, preferably up to 1 wt .-% and particularly preferably up to 0, Contain 5 wt .-% of impurities, each based on the total weight of the employed 4,4'-dichlorodiphenyl sulfone or of the used 4,4'-Difluordiphenylsulfons.
- the impurities which may be present are included in the percentage by weight with respect to component (A1).
- component (A1) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 98% by weight of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone, based on the total weight of component (A1) in the reaction mixture (R G ).
- the percentages by weight with respect to component (A1) also refer to the sum of the 4,4'-dichlorodiphenylsulfone used and the 4,4'-difluorodiphenylsulfone used.
- the component (A1) may further contain other dihalogen compounds other than 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone.
- Component (A1) contains not more than 50% by weight, preferably not more than 20% by weight, more preferably not more than 10% by weight and in particular not more than 2% by weight of other dihalogen compounds.
- component (A1) contains at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of 4,4'-dichlorodiphenyl sulfone.
- reaction mixture (R G ) contains no further dihalogen compounds in addition to the dihalogen compounds of component (A1).
- the present invention thus also provides a process in which the reaction mixture (R G ) contains no further dihalogen compounds in addition to the dihalogen compounds of component (A1).
- component (A1) consists essentially of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.
- component (A1) more than 99 wt.%, Preferably more 99.5 wt .-%, particularly preferably more than 99.9 wt .-% of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, in each case based on the total weight of component (A1) in the reaction mixture (R G ).
- 4,4'-dichlorodiphenyl sulfone is particularly preferred as component (A1).
- component (A1) consists essentially of 4,4'-dichlorodiphenylsulfone. In a further particularly preferred embodiment, component (A1) consists of 4,4'-dichlorodiphenylsulfone.
- the reaction mixture (R G ) contains as component (B1), which is also referred to as dihydroxy component, at least one dihydroxy compound.
- component (B1) which is also referred to as dihydroxy component, at least one dihydroxy compound.
- at least one dihydroxy compound is meant in the present case exactly one dihydroxy compound and mixtures of two or more dihydroxy compounds.
- the component (B1) may thus be both a single dihydroxy compound and mixtures of two or more dihydroxy compounds.
- component (B1) contains at least 50% by weight of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 4,4'-dihydroxybenzophenone and hydroquinone, based on the total weight of component (B1) in the reaction mixture (R G ).
- the percentages by weight with respect to component (B1) also relate to the sum of the 4,4'-dihydroxydiphenylsulfone used, bisphenol A (2,2-bis- (4-hydroxyphenyl) -propane), 4,4'- Dihydroxybenzophenone and hydroquinone.
- 4,4'-dihydroxydiphenylsulfone and bisphenol A are preferable, with bisphenol A being particularly preferred.
- the 4,4'-dihydroxydiphenylsulfone, the bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), the 4,4'-dihydroxybenzophenone and the hydroquinone can be used as pure substance or as a technical product, the bis 2% by weight, preferably up to 1% by weight and more preferably up to 0.5% by weight of impurities, in each case based on the total weight of the 4,4'-dihydroxydiphenylsulfone used, of the bisphenol A used ( 2,2-bis (4-hydroxyphenyl) propane), the 4,4'-dihydroxybenzophenone used and the hydroquinone used.
- the impurities which may be present are included in the percentage by weight with respect to component (B1).
- component (B1) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 98% by weight of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A. (2,2-bis (4-hydroxyphenyl) propane), 4,4'-dihydroxybenzophenone and hydroquinone, based on the total weight of component (B1) in the reaction mixture (R G ).
- the percentages by weight with respect to component (B1) also relate to the sum of the 4,4'-dihydroxydiphenylsulfone used, bisphenol A (2,2-bis- (4-hydroxyphenyl) -propane), 4,4'- Dihydroxybenzophenone and hydroquinone.
- the component (B1) may further contain other dihydroxy compounds other than 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 4,4'-dihydroxybenzophenone and hydroquinone.
- the component (B1) contains not more than 50% by weight, preferably not more than 20% by weight, more preferably not more than 10% by weight and in particular not more than 2% by weight of other dihydroxy compounds.
- phenolic hydroxy group is meant according to the invention a hydroxy group (-OH) which is bonded to an aromatic system.
- Suitable other dihydroxy compounds are, for example, resorcinol (1,3-dihydroxybenzene), dihydroxynaphthalenes, bisphenol TMC (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane), bisphenol AF (2,2-bis (4-bis) hydroxyphenyl) hexafluoropropane), 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclopentane and / or 4,4'-dihydroxybiphenyl.
- component (B1) contains at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of bisphenol A.
- component (B1) contains at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of 4,4'-dihydroxydiphenylsulfone.
- reaction mixture (R G ) contains no further dihydroxy compounds in addition to the dihalogen compounds of component (B1).
- the present invention thus also provides a process in which the reaction mixture (R G ) contains no further dihydroxy compounds in addition to the dihalogen compounds of component (B1).
- component (B1) consists essentially of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 4 , 4'-Dihydroxybenzophenone and hydroquinone.
- component (B1) more than 99 wt.%, Preferably more 99.5 wt .-%, particularly preferably more than 99.9 wt .-% of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), 4,4'-dihydroxybenzophenone and hydroquinone, each based on the total weight of component (B1) in the reaction mixture (R G ).
- bisphenol A and 4,4'-dihydroxydiphenylsulfone are particularly preferred as component (B1), with bisphenol A being most preferred.
- component (B1) consists essentially of bisphenol A. In a further particularly preferred embodiment, component (B1) consists of bisphenol A.
- reaction mixture (R G ) as component (C) contains potassium carbonate
- the hydroxy groups of the dihydroxy compounds used as component (B1) in the reaction mixture (R G ) may be partially present in deprotonated form.
- reaction mixture (R G ) does not contain 4,4'-dihydroxybiphenyl.
- the reaction mixture (R G ) contains as component (C), which is also referred to as carbonate component, potassium carbonate.
- component (C) which is also referred to as carbonate component, potassium carbonate.
- the potassium carbonate is preferably anhydrous.
- component (C) contains at least 50% by weight of potassium carbonate having a volume-average particle size of ⁇ 25 ⁇ m, based on the total weight of component (C) in the reaction mixture (R G ).
- the potassium carbonate can be used as a pure substance or as a technical product, which may contain up to 2 wt .-%, preferably up to 1 wt .-% and particularly preferably up to 0.5 wt .-% impurities, each based on the total weight of the potassium carbonate used.
- the impurities which may be present in the potassium carbonate are included in the percentage by weight with respect to component (C).
- component (C) contains at least 80 wt .-%, preferably at least 90 wt .-% and particularly preferably at least 98 wt .-% potassium carbonate having a volume-average particle size of ⁇ 25 microns, based on the total weight of the component (B1 ) in the reaction mixture (R G ).
- the component (C) may further contain other carbonate compounds other than potassium carbonate.
- Component (C) contains not more than 50% by weight, preferably not more than 20% by weight, more preferably not more than 10% by weight and in particular not more than 2% by weight of other carbonate compounds.
- ammonium carbonate ammonium bicarbonate
- lithium carbonate lithium hydrogen carbonate
- sodium carbonate sodium hydrogen carbonate
- potassium bicarbonate alkaline earth carbonates
- Erdalkalihydrogenkarbonate can be used.
- component (C) consists essentially of potassium carbonate.
- component (C) contains more than 99% by weight, preferably more than 99.5% by weight, particularly preferably more than 99.9% by weight of potassium carbonate, in each case based on the total weight of component (C) in the reaction mixture (R G ).
- component (C) consists of potassium carbonate.
- reaction mixture (R G ) in addition to the component (C) contains no further carbonate compounds, in particular no sodium carbonate or sodium bicarbonate.
- reaction mixture (R G ) contains no sodium carbonate and no sodium bicarbonate.
- Potassium carbonate is preferred as the potassium carbonate with a volume-weighted average particle size (D [4,3]) of less than 25 microns.
- the volume-weighted average particle size (D [4,3]) of the potassium carbonate is determined using a particle size measuring device in a suspension of the potassium carbonate in a mixture of chlorobenzene and sulfolane.
- the volume-average particle size (D [4,3]) can be determined, for example, with a Mastersizer 2000 from Malvern on a suspension of the particles in chlorobenzene / sulfolane (60/40).
- potassium carbonate having a volume-average particle size (D [4,3]) less than 15 microns.
- Particularly preferred potassium carbonate has a volume-average particle size (D [4,3]) in the range from 20 nm to ⁇ 25 ⁇ m.
- preferred potassium carbonate has a volume-average particle size in the range of 20 nm to 15 microns.
- the present invention thus also provides a process in which the potassium carbonate has a volume-average particle size in the range from 20 nm to ⁇ 25 ⁇ m, preferably in the range from 20 nm to 15 ⁇ m.
- reaction mixture (R G ) contains at least one aprotic polar solvent as component (D).
- at least one aprotic polar Solvent are understood according to the invention exactly an aprotic polar solvent and mixtures of two or more aprotic polar solvents.
- aprotic polar solvent for example, anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and mixtures of these solvents are suitable.
- aprotic polar solvent N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and mixtures of these solvents are preferred. Particularly preferred as the aprotic polar solvent is N-methyl-2-pyrrolidone.
- the present invention thus also provides a process in which the reaction mixture (R G ) as component (D) at least one aprotic polar solvent selected from the group consisting of anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and Contains N-ethyl-2-pyrrolidone.
- aprotic polar solvent selected from the group consisting of anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and Contains N-ethyl-2-pyrrolidone.
- the present invention thus also provides a process in which the reaction mixture (R G ) contains N-methyl-2-pyrrolidone as component (D).
- component (D) contains at least 50 wt .-% of at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, based on the total weight of component (D) in Reaction mixture (R G ).
- N-methyl-2-pyrrolidone is particularly preferred.
- component (D) consists essentially of at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
- component (D) more than 99 wt .-%, more preferably more than 99.5 wt .-%, particularly preferably more than 99.9 wt .-% of at least one aprotic polar solvent selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, in each case based on the total weight of component (D) in the reaction mixture (R G ), where N-methyl-2- Pyrrolidone is preferred.
- component (D) consists of N-methyl-2-pyrrolidone.
- N-methyl-2-pyrrolidone is also referred to as NMP or N-methylpyrrolidone.
- reaction mixture contains, in addition to the aprotic polar solvents of component (D), no further aprotic polar solvents.
- reaction mixture (R G) in which the component (A1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1) in the reaction mixture (R G ) component (B1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dihydroxydiphenylsulfone, based on the total weight of component (B1) in the reaction mixture (R G ) the component (C) consists essentially of potassium carbonate having a volume-average particle size of ⁇ 25 microns, and the component (D) consists essentially of N-methylpyrrolidone.
- the component (A1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1)
- reaction mixture (R G ) in which the component (A1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1) in the reaction mixture (R G )
- component (B1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of bisphenol A, based on the total weight of component (B1) in the reaction mixture (R G )
- the component (C) consists essentially of potassium carbonate having a volume-average particle size of ⁇ 25 microns
- the component (D) consists essentially of N-methylpyrrolidone.
- the ratio of components (A1) and (B1) in the reaction mixture (R G ) can vary within wide limits.
- the molar ratio of component (B1) to (A1) is preferably in the range from 0.95 to 1.05 to 1, preferably in the range from 0.97 to 1.03 to 1.
- the reaction mixture (R G ) is reacted under conditions of the so-called carbonate method.
- the reaction (polycondensation reaction) is generally carried out at temperatures in the range of 80 to 250 ° C, preferably in the range of 100 to 220 ° C, wherein the upper limit of the temperature by the boiling point of the aprotic polar solvent (component D) at atmospheric pressure (1013 , 25 mbar).
- the reaction is generally carried out at atmospheric pressure.
- the reaction is preferably carried out in a time interval of 2 to 12 hours, in particular in the range of 3 to 10 hours.
- the isolation of the polyarylene ether sulfone polymer obtained according to the invention can be carried out, for example, by precipitation of the polymer solution in water or mixtures of water with further solvents.
- the precipitated polyarylene ether sulfone polymer can then be extracted with water and then dried.
- the precipitation can also be carried out in an acidic medium.
- Suitable acids are, for example, organic or inorganic acids, for example carboxylic acids such as acetic acid, propionic acid, succinic acid or citric acid, and mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.
- the process according to the invention gives polyarylene ether sulfone polymers having low polydispersities (Q).
- the present invention thus also provides a polyarylene ether sulfone polymer obtainable by the process according to the invention.
- the polyarylene ether sulfone polymer generally has a polydispersity (Q) of ⁇ 4, preferably ⁇ 3.5.
- the polydispersity (Q) is defined as the quotient of the weight-average molecular weight (Mw) and the number-average molecular weight (M n ).
- the polydispersity (Q) of the polyarylene ether sulfone polymer is in the range of 2.0 to ⁇ 4, preferably in the range of 2.0 to ⁇ 3.5.
- the weight-average molecular weight (M w ) and the number-average molecular weight (M n ) are measured by gel permeation chromatography.
- the polydispersity (Q) and the average molecular weights of the polyarylene ether sulfone polymer were measured by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- DMAc dimethylacetamide
- Preferred polyarylene ether sulfone polymers are those which contain at least one of the following building blocks la to Ib as recurring structural units:
- polyarylene ether sulfone polymer is essentially composed of at least one kind of building blocks selected from the group Ia and Ib.
- polysulfone polymers which are composed of repeating units of the formula Ia. These polyarylene ether sulfone polymers are also referred to as polysulfone (PSU).
- polyarylene ether sulfone polymers which are composed of repeating units of the formula Ib. These polyarylene ether sulfone polymers are also referred to as polyethersulfone (PESU).
- PESU polyethersulfone
- PESU and PSU correspond in the context of the present invention to DIN EN ISO 1043-1 (Plastics - Coding Letters and Abbreviations - Part 1: Basic Polymers and their Special Properties (ISO 1043-1: 2001); 1: 2002).
- the polyarylene ether sulfone polymer obtainable by the process according to the invention generally has weight-average molecular weights (M w ) of from 10 000 to 150 000 g / mol, preferably in the range from 15 000 to 120 000 g / mol, particularly preferably in the range from 18 000 to 100 000 g / mol.
- Mw weight average molecular weights
- the weight average Molecular weights (Mw) are measured by gel permeation chromatography (GPC). The measurement is carried out as described above.
- the polyarylene ether sulfone polymers generally have either halogen end groups, in particular chlorine end groups, or etherified end groups, in particular alkyl ether end groups.
- the etherified end groups can be obtained by reacting the OH or phenolate end groups with suitable etherifying agents.
- Suitable etherifying agents are, for example, monofunctional alkyl or aryl halide, for example C 1 -C 6 -alkyl chloride, bromide or iodide, preferably methyl chloride, or benzyl chloride, bromide or iodide or mixtures thereof.
- Preferred end groups of the polyarylene ether sulfone polymers according to the invention are halogen end groups, in particular chlorine, and alkoxy end groups, in particular methoxy, aryloxy end groups, in particular phenoxy, or benzyloxy.
- polyarylene ether sulfone polymers especially linear polyarylene ether sulfone polymers
- PVP polyvinylpyrrolidone
- the DE-A 10 2005 001 599 describes functionalized, branched polyarylene ether sulfone copolymers containing sulfonated and non-sulfonated units.
- the sulfonated polyarylene ether sulfone copolymers are prepared by sulfonation from the corresponding branched polyarylene ether sulfone copolymers.
- the publication mentions the use of the sulfonated copolymers to make membranes.
- polymer blends of the aforementioned sulfonated polyarylene ether sulfone copolymers and numerous blend partners are mentioned, among other things, polyvinylpyrrolidone is enumerated.
- the DE-A 10 2005 001 599 does not disclose blends of non-sulfonated branched polyarylene ether sulfone polymers, nor does it address the particular requirements of use for producing hollow fiber membranes.
- polyarylene ether sulfone polymers are not sulfonated in the inventive processes for preparing the polyarylene ether sulfone polymers.
- the according to the According to the invention available polyarylene ether sulfone polymers thus no free sulfonic acid groups.
- EP 0 509 663 B2 Dialysis modules with selectively permeable hollow fiber membranes based on a mixture of polyethersulfone and a hydrophilic polymer such as polyvinylpyrrolidone or polyethylene glycol.
- the EP 0 615 778 A1 discloses a process for producing hydrophilic membranes using hydrophobic polymers such as polyethersulfones and hydrophilic polymers using polyvinylpyrrolidone.
- At least one hydrophilic polymer may be added to the solution provided in step (i).
- a suitable hydrophilic polymer is, for example, polyvinylpyrrolidone having a weight average molecular weight (M w ) in the range of 10,000 to 2,000,000 g / mol, preferably in the range of 200,000 to 1,600,000 g / mol.
- a solution of the polyarylene ether sulfone polymer and optionally the hydrophilic polymer in an aprotic polar solvent is provided.
- Suitable aprotic polar solvents are those in which the polyarylene ether sulfone polymers are soluble, "soluble" meaning that at room temperature (20 ° C.) at least 10% by weight, preferably at least 20% by weight, in particular at least 25% by weight of the polyarylene ether-sulfone polymer based on the total weight of the solution in the aprotic polar solvent.
- the solution obtained in step (i) is degassed prior to performing step (ii).
- the person skilled in the art chooses customary, generally known methods for degassing liquids.
- Preferred aprotic polar solvents for providing the solution in step (i) are N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, dimethylformamide and sulfolane (tetrahydrothiophene-1,1-dioxide). Particularly preferred are N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, and dimethylformamide.
- the preparation of the solution in step (i) can be carried out in conventional containers, in particular in those which comprise a stirring device and preferably a device for temperature control.
- the solution according to step (i) of the process according to the invention is preferably carried out with stirring.
- the dissolution of the polyarylene ether sulfone polymer according to the invention and optionally of the hydrophilic polymer can be carried out successively or simultaneously.
- the duration of step (i) can vary within a wide range.
- the duration of step (i) is preferably from 10 minutes to 48 hours, in particular from 10 minutes to 12 hours, particularly preferably from 15 minutes to 6 hours.
- the skilled person chooses the duration of step (i), so that a homogeneous solution of the Polyarylene ether sulfone polymer according to the invention and optionally the hydrophilic polymer is obtained in the aprotic polar solvent.
- step (i) at elevated temperature, in particular from 20 ° C to 120 ° C, preferably from 40 ° C to 100 ° C.
- elevated temperature in particular from 20 ° C to 120 ° C, preferably from 40 ° C to 100 ° C.
- the skilled person selects the temperature in particular as a function of the aprotic polar solvent.
- the preferred concentration of the polyarylene ether sulfone polymer according to the invention and optionally of the hydrophilic polymer in the aprotic polar solvent depends in particular on the nature of step (ii).
- the solution provided in step (i) contains from 5 to 40% by weight, in particular from 10 to 30% by weight, of the polyarylene ether sulfone polymer according to the invention, based on the total weight of the solution.
- the sum of the polyarylene ether sulfone polymer of the present invention and the hydrophilic polymer is 5 to 40% by weight, more preferably 10 to 30% by weight, based on Total weight of the solution.
- the weight% ratio of polyarylene ether sulfone polymer to hydrophilic polymer in the solution in step (i) is generally in the range of 98 to 2 to 50 to 50.
- step (ii) the separation of the polyarylene ether sulfone polymer according to the invention or the mixture of the polyarylene ether sulfone polymer according to the invention and the hydrophilic polymer from the aprotic polar solvent takes place to form a membrane.
- the shape of the membrane may vary, the membrane being present in particular in the form of a film, in the form of a layer on a carrier or in the form of a fiber.
- the membrane according to the present invention is a hollow-fiber membrane, in particular a hollow-fiber membrane for dialysis applications.
- step (ii) is preferably carried out by wet spinning, that is to say the solution prepared in step (i) is wet-spun into a fiber in step (ii). If a wet spinning process is used in step (ii), a dry jet wet spinning process is particularly preferred.
- core liquid is to be understood as meaning a liquid which comes into contact with the solution provided in step (i) in the core of the spinneret.
- the core liquid has coagulating properties and serves to stabilize the core of the hollow fiber during the wet spinning process.
- the distance between the nozzle and the coagulation liquid in the coagulation bath is referred to as the drying zone and is preferably from 0.1 to 100 cm, in particular from 0.5 to 50 cm, preferably from 1 to 30 cm.
- the structure of the pores in the hollow fiber membrane is influenced by the coagulation liquid in which the polyarylene ether sulfone polymer according to the invention or the mixture of the inventive polyarylene ether sulfone polymer and the hydrophilic polymer is preferably not or not completely soluble.
- the coagulation liquid causes at least partial precipitation of the polymer to be spun in the coagulation bath in the form of a fiber.
- Suitable coagulation liquids and core liquids are preferably liquids which are completely miscible with the aprotic polar solvent of the solution provided in step (i) provided that the inventive polyarylene ether sulfone polymer or the mixture of the inventive polyarylene ether sulfone polymer and the hydrophilic polymer in which coagulation liquid is not or partially insoluble.
- nucleation and coagulation liquid with respect to the aprotic polar solvent of the solution provided in step (i) such that the liquids are, on the one hand, miscible and, on the other hand, separable, ie recoverable in pure form, after spinning a distillative separation is preferred.
- the core liquid used is preferably a mixture of the aprotic polar solvent and deionized water, in particular N-methylpyrrolidone and water.
- the mixing ratio (weight ratio) of NMP to water is preferably from 15: 1 to 1:15, more preferably from 5: 1 to 1: 5, especially from 2: 1 to 1: 2.
- the coagulation liquid used is preferably at least one aliphatic alcohol or water or a mixture of the two abovementioned compounds.
- an aliphatic alcohol in particular ethanol or isopropanol, optionally mixed with water, and water in a second coagulation bath.
- the polyarylene ether sulfone polymer according to the invention is preferably used in the process according to the invention for producing a membrane in anhydrous form.
- anhydrous is meant that the water content in the solution provided in step (i) is less than 5% by weight, preferably less than 2% by weight, in particular less than 1% by weight, based on the Total weight of the solution.
- steps (i) and (ii) of the process according to the invention optionally, (iii) the preparation of the membrane is carried out, wherein one or more steps selected from purification, washing out and postcrosslinking are carried out under treatment.
- the present invention also relates to the membrane obtainable by the process according to the invention.
- the membranes according to the invention in particular the hollow-fiber membranes according to the invention, have a high mechanical load-bearing capacity Continuous use. They have a low exclusion limit in ultrafiltration, in particular dialysis.
- the present invention also relates to a membrane comprising the polyarylene ether sulfone polymer according to the invention. Further subject of the present invention is a membrane, obtainable by the process according to the invention for producing a membrane.
- the present invention thus also relates to a hollow fiber for dialysis, which is obtainable by the process according to the invention.
- the present invention furthermore relates to the use of the polyarylene ether sulfone polymer obtainable by the process according to the invention for the production of membranes.
- the viscosity number VZ was measured according to DIN ISO 1628-1 in a 1% strength by weight NMP solution at 25.degree.
- the isolation of the polyarylethersulfone polymers is carried out by grafting a NMP solution of the polymers in demineralized water at room temperature (20 ° C). The drop height is 0.5 m. The throughput is approx. 2.5 l per hour. The resulting beads are then extracted at 85 ° C for twenty hours with water (water flow 160 l / h). Thereafter, the beads are dried at a temperature below the glass transition temperature T g to a residual moisture content of less than 0.1 wt .-%.
- the volume-average particle size (D [4,3]) of the potassium carbonate or sodium carbonate used was determined using a Mastersizer 2000 from Malvern on a suspension of the particles in chlorobenzene / sulfolane (60/40).
- the molecular weight distribution of the polyarylethersulfone polymers was determined by GPC measurement in DMAc.
- the molecular weights of the polyarylethersulfone polymers were also characterized by viscosity measurements (1 wt.% Solution in NMP).
- the proportion of cyclic dimer was determined by HPLC with THF as the liquid phase and PLGEL ® columns.
- PVP polyvinylpyrrolidone
- the composition of the core liquid was 55:45 parts by weight NMP: deionized water.
- the distance between the spinneret and the precipitation bath was 20 cm.
- a 2-stage precipitation process with isopropanol was used as first coagulation liquid in the first precipitation bath and water as second coagulation liquid in the second precipitation bath.
- the take-off speed of the fibers was equal to the spinning speed (8.6 cm / s).
- the fibers were stored in water for 3 days. Before the tensile strain measurement, the fibers are removed from the water, externally adhering water is removed, then the samples are stored for 48 hours at 23 ° C and 50% relative humidity. Thereafter, the fibers are cut to a length of 150 mm and pulled in a Zwick / Roell tensile-stretching apparatus Z010 at a strain rate of 20 mm / min to break.
- the polyarylene ether sulfone polymers according to the invention have comparable viscosity numbers (VZ) but a narrower molecular weight distribution for a shorter reaction time. Surprisingly, hollow fiber membranes produced from these polyarylene ether sulfone polymers have better mechanical properties.
- V4 and V5 show that the use of sodium carbonate does not achieve sufficient molecular weight buildup, therefore no further analyzes were performed.
- Example V6 shows that PPSU has a broader molecular weight distribution. Under the experimental conditions chosen for V1, 2 and 3, no hollow fiber membrane could be produced from the polyarylene ether sulfone polymer according to Example V6.
Abstract
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Polyarylenethersulfon-Polymers durch Umsetzung eines Reaktionsgemischs (R G ) enthaltend eine Dihalogenkomponente (A1), eine Dihydroxykomponente (B1) und Kaliumcarbonat (C1) mit einer volumenmittleren Partikelgröße von < 25 µm. Darüber hinaus betrifft die vorliegende Erfindung die nach dem Verfahren erhältlichen Polyarylenethersulfon-Polymere sowie aus dem Polyarylenethersulfon-Polymer erhältliche Produkte sowie Membranen, die aus dem Polyarylenethersulfon-Polymer hergestellt werden.The present invention relates to a process for preparing a polyarylene ether sulfone polymer by reacting a reaction mixture (R G) containing a dihalogen component (A1), a dihydroxy component (B1) and potassium carbonate (C1) having a volume-average particle size of <25 microns. Moreover, the present invention relates to the polyarylene ether sulfone polymers obtainable by the process and to products obtainable from the polyarylene ether sulfone polymer, as well as membranes made from the polyarylene ether sulfone polymer.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Polyarylenethersulfon-Polymers durch Umsetzung eines Reaktionsgemischs (RG) enthaltend eine Dihalogenkomponente (A1), eine Dihydroxykomponente (B1) und Kaliumcarbonat (C1) mit einer volumenmittleren Partikelgröße von < 25 µm. Darüber hinaus betrifft die vorliegende Erfindung die nach dem Verfahren erhältlichen Polyarylenethersulfon-Polymere sowie aus dem Polyarylenethersulfon-Polymer erhältliche Produkte sowie Membranen, die aus dem Polyarylenethersulfon-Polymer hergestellt werden.The present invention relates to a process for preparing a polyarylene ether sulfone polymer by reacting a reaction mixture (R G ) containing a dihalogen component (A1), a dihydroxy component (B1) and potassium carbonate (C1) having a volume-average particle size of <25 microns. In addition, the present invention relates to the polyarylene ether sulfone polymers obtainable by the process and to products obtainable from the polyarylene ether sulfone polymer and to membranes made from the polyarylene ether sulfone polymer.
Polyarylenethersulfon-Polymere gehören zur Gruppe der Hochleistungsthermoplaste und zeichnen sich durch hohe Wärmeformbeständigkeit, gute mechanische Eigenschaften und inhärente Flammwidrigkeit aus (
Die Herstellung der Polyarylenethersulfon-Polymere kann unter anderem entweder über die Hydroxid-Methode, bei der zuerst aus der Dihydroxykomponente und dem Hydroxid ein Salz hergestellt wird, oder über die sogenannte Carbonat-Methode erfolgen.
Allgemeine Hinweise zur Herstellung der Polyarylenethersulfon-Polymere nach der Hydroxid-Methode finden sich u.a. bei
General information on the preparation of the polyarylene ether sulfone polymers by the hydroxide method can be found, inter alia
Verfahren zur Herstellung von Polyarylenethersulfon-Polymeren aus aromatischen Bishalogenverbindungen und aromatischen Bisphenolen oder deren Salzen in Gegenwart mindestens eines Alkalimetall- oder Ammoniumcarbonats oder -hydrogencarbonats in einem aprotischen Lösungsmittel sind dem Fachmann bekannt und werden beispielsweise in
Die Herstellung von Hochleistungsthermoplasten wie Polyarylenethersulfon-Polymeren erfolgt durch Polykondensationsreaktionen, die üblicherweise bei hoher Reaktionstemperatur in dipolar aprotischen Lösungsmitteln, wie beispielweise DMF, DMAc, Sulfolan, DMSO und NMP durchgeführt werden.The production of high-performance thermoplastics such as polyarylene ether sulfone polymers is carried out by polycondensation reactions, which are usually carried out at high reaction temperature in dipolar aprotic solvents such as DMF, DMAc, sulfolane, DMSO and NMP.
Anwendungen von Polyarylenethersulfon-Polymeren in Polymermembranen gewinnen zunehmend an Bedeutung.Applications of polyarylene ether sulfone polymers in polymer membranes are becoming increasingly important.
In der
In der
Der vorliegenden Erfindung liegt somit die Aufgabe zugrunde, ein Verfahren zur Herstellung von Polyarylenethersulfon-Polymeren bereitzustellen, das die Nachteile der im Stand der Technik beschriebenen Verfahren nicht oder nur in vermindertem Maße aufweist. Das Verfahren soll innerhalb von kurzen Reaktionszeiten durchführbar sein. Die nach dem Verfahren erhältlichen Polyarylenethersulfon-Polymere sollen eine geringe Polydispersität sowie gute mechanische Eigenschaften, insbesondere im Hinblick auf Membrananwendungen, aufweisen. Darüber hinaus soll das Verfahren innerhalb kurzer Reaktionszeiten einen guten Molekulargewichtsaufbau ermöglichen. Gelöst wird diese Aufgabe durch ein Verfahren zur Herstellung eines Polyarylenethersulfon-Polymers durch Umsetzen eines Reaktionsgemischs (RG) enthaltend die Komponenten:
- (A1) eine Dihalogenkomponente, die mindestens 50 Gew.-% mindestens einer Dihalogenverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG),
- (B1) eine Dihydroxykomponente, die mindestens 80 Gew.-% mindestens einer Dihydroxyverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dihydroxydiphenylsulfon, Bisphenol A, 4,4'-Dihydroxybenzophenon und Hydrochinon enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG),
- (C) eine Karbonatkomponente, die mindestens 50 Gew.-% Kaliumcarbonat enthält, das eine volumengemittelte Partikelgröße von < 25 µm aufweist, bezogen auf das Gesamtgewicht der Komponente (C) im Reaktionsgemisch (RG).
- (A1) a dihalogen component containing at least 50% by weight of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone, based on the total weight of component (A1) in the reaction mixture (R G ),
- (B1) a dihydroxy component containing at least 80% by weight of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A, 4,4'-dihydroxybenzophenone and hydroquinone, based on the total weight of component (B1 ) in the reaction mixture (R G ),
- (C) a carbonate component containing at least 50 wt .-% potassium carbonate having a volume average particle size of <25 microns, based on the total weight of component (C) in the reaction mixture (R G ).
Weiterhin Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines Polyarylenethersulfon-Polymers durch Umsetzen eines Reaktionsgemischs (RG) enthaltend die Komponenten:
- (A1) eine Dihalogenkomponente, die mindestens 50 Gew.-% mindestens einer Dihalogenverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG),
- (B1) eine Dihydroxykomponente, die mindestens 50 Gew.-% mindestens einer Dihydroxyverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dihydroxydiphenylsulfon, Bisphenol A, 4,4'-Dihydroxybenzophenon und Hydrochinon enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG),
- (C) eine Karbonatkomponente, die mindestens 50 Gew.-% Kaliumcarbonat enthält, das eine volumengemittelte Partikelgröße von < 25 µm aufweist, bezogen auf das Gesamtgewicht der Komponente (C) im Reaktionsgemisch (RG).
- (A1) a dihalogen component containing at least 50% by weight of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone, based on the total weight of component (A1) in the reaction mixture (R G ),
- (B1) a dihydroxy component containing at least 50% by weight of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A, 4,4'-dihydroxybenzophenone and hydroquinone, based on the total weight of component (B1 ) in the reaction mixture (R G ),
- (C) a carbonate component containing at least 50 wt .-% potassium carbonate having a volume average particle size of <25 microns, based on the total weight of component (C) in the reaction mixture (R G ).
Bei den im Stand der Technik beschriebenen Verfahren zur Herstellung von Polyarylenethersulfon-Polymeren werden meist sehr breite Molekulargewichtsverteilungen erhalten. Ein Maß für die Molekulargewichtsverteilung ist die Polydispersität (Q). Die Polydispersität (Q) ist definiert als Quotient aus dem gewichtsmittleren Molekulargewicht (Mw) und dem zahlenmittleren Molekulargewicht (Mn). Bei den im Stand der Technik beschriebenen Verfahren werden meist Polydispersitäten (Q) von deutlich größer als 3,5 erhalten. Polyarylenethersulfon-Polymere mit Polydispersitäten (Q) von > 4 sind insbesondere zur Herstellung von Membranen nur bedingt geeignet.In the process described in the prior art for the preparation of polyarylene ether sulfone polymers usually very broad molecular weight distributions are obtained. A measure of the molecular weight distribution is the polydispersity (Q). The polydispersity (Q) is defined as the quotient of the weight average molecular weight (Mw) and number average molecular weight (M n ). Polydispersities (Q) of significantly greater than 3.5 are usually obtained in the processes described in the prior art. Polyarylene ether sulfone polymers having polydispersities (Q) of> 4 are of limited use, in particular, for the production of membranes.
Aus der Literatur ist weiterhin bekannt (
Ziel der Erfindung ist es darüber hinaus, ein Verfahren zur Verfügung zu stellen, bei dem zyklische Oligomere nicht abgetrennt werden müssen. Die erfindungsgemäße Aufgabe wird durch das erfindungsgemäße Verfahren gelöst.The aim of the invention is moreover to provide a process in which cyclic oligomers need not be separated. The object of the invention is achieved by the method according to the invention.
Zur Herstellung des erfindungsgemäßen Polyarylenethersulfon-Polymers wird ein Reaktionsgemisch (RG) umgesetzt, welches die vorstehend beschriebenen Komponenten (A1), (B1), (C) und gegebenenfalls (D) enthält. Die Komponenten (A1) und (B1) gehen dabei eine Polykondensationsreaktion ein.To prepare the polyarylene ether sulfone polymer according to the invention, a reaction mixture (R G ) is reacted which contains the above-described components (A1), (B1), (C) and optionally (D). The components (A1) and (B1) enter into a polycondensation reaction.
Die Komponente (D) dient als Lösungsmittel. Die Komponente (C) dient als Base, um die Komponente (B1) während der Kondensationsreaktion zu deprotonieren.Component (D) serves as a solvent. Component (C) serves as a base to deprotonate component (B1) during the condensation reaction.
Unter Reaktionsgemisch (RG) wird dabei das Gemisch verstanden, das im erfindungsgemäßen Verfahren zur Herstellung des Polyarylenethersulfon-Polymers eingesetzt wird. Vorliegend beziehen sich alle Angaben in Bezug auf das Reaktionsgemisch (RG) somit auf das Gemisch, das vor der Polykondensation vorliegt. Während des erfindungsgemäßen Verfahrens findet die Polykondensation statt, wobei sich das Reaktionsgemisch (RG) durch Polykondensation der Komponenten (A1) und (B1) zum Zielprodukt, dem Polyarylenethersulfon-Polymer, umsetzt. Das nach der Polykondensation erhaltene Gemisch, welches das Zielprodukt, das Polyarylenethersulfon-Polymer, enthält, wird auch als Produktgemisch (PG) bezeichnet.Under reaction mixture (R G ) is understood to mean the mixture which is used in the process according to the invention for the preparation of the polyarylene ether sulfone polymer. In the present case, all data relating to the reaction mixture (R G ) thus refer to the mixture which is present before the polycondensation. During the process according to the invention, the polycondensation takes place, wherein the reaction mixture (R G ) by polycondensation of the components (A1) and (B1) to the target product, the polyarylene ether sulfone polymer, is reacted. The mixture obtained after the polycondensation, which contains the target product, the polyarylene ether sulfone polymer, is also referred to as a product mixture (P G ).
In der Regel werden die Komponenten des Reaktionsgemischs (RG) gemeinsam zur Reaktion gebracht. Die einzelnen Komponenten können dabei in einem vorgelagerten Schritt gemischt und anschließend zur Reaktion gebracht werden. Es ist auch möglich, die Einzelkomponenten einem Reaktor zuzuführen, in dem diese gemischt werden und nachfolgend zur Reaktion gebracht werden.In general, the components of the reaction mixture (R G ) are reacted together. The individual components can be in an upstream Step mixed and then reacted. It is also possible to feed the individual components to a reactor in which they are mixed and subsequently reacted.
Bei dem erfindungsgemäßen Verfahren werden die einzelnen Komponenten des Reaktionsgemischs (RG) im Allgemeinen gemeinsam umgesetzt. Die Umsetzung erfolgt dabei bevorzugt einstufig. Das heißt, die Deprotonierung der Komponente (B1) sowie die Kondensationsreaktion zwischen den Komponenten (A1) und (B1) erfolgt in einer einzigen Reaktionsstufe, ohne dass Zwischenprodukte, wie beispielsweise die deprotonierten Spezies der Komponente (B1) isoliert werden.In the process according to the invention, the individual components of the reaction mixture (R G ) are generally reacted together. The reaction is preferably carried out in one stage. That is, the deprotonation of the component (B1) and the condensation reaction between the components (A1) and (B1) takes place in a single reaction stage, without isolated intermediates, such as the deprotonated species of component (B1).
Als Komponente (A1), die auch als Dihalogenkomponente bezeichnet wird, enthält das Reaktionsgemisch (RG) mindestens eine Dihalogenverbindung. Unter "mindestens eine Dihalogenverbindung" werden vorliegend genau eine Dihalogenverbindung sowie Gemische aus zwei oder mehreren Dihalogenverbindungen verstanden.As component (A1), which is also referred to as dihalogen component, the reaction mixture (R G ) contains at least one dihalogen compound. By "at least one dihalogen compound" is meant in the present case exactly one dihalogen compound and mixtures of two or more dihalogen compounds.
Bei der Komponente (A1) kann es sich somit sowohl um eine einzelne Dihalogenverbindung, als auch um eine Mischung aus zwei oder mehreren Dihalogenverbindungen handeln.The component (A1) can thus be both a single dihalogen compound and a mixture of two or more dihalogen compounds.
Es ist erfindungswesentlich, dass die Komponente (A1) mindestens 50 Gew.-% mindestens einer Dihalogenverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG). Die Gewichtsprozentangaben in Bezug auf die Komponente (A1) beziehen sich dabei darüber hinaus auf die Summe des eingesetzten 4,4'-Dichlordiphenylsulfons und des eingesetzten 4,4'-Difluordiphenylsulfons. Unter 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon ist das 4,4'-Dichlordiphenylsulfon bevorzugt.It is essential to the invention that component (A1) contains at least 50% by weight of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, based on the total weight of component (A1) in the formula Reaction mixture (R G ). The percentages by weight with respect to component (A1) also refer to the sum of the 4,4'-dichlorodiphenylsulfone used and the 4,4'-difluorodiphenylsulfone used. Among 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone, 4,4'-dichlorodiphenylsulfone is preferred.
Das 4,4'-Dichlordiphenylsulfon und das 4,4'-Difluordiphenylsulfon können dabei als Reinstoff oder als technisches Produkt eingesetzt werden, das bis zu 2 Gew.-%, bevorzugt bis zu 1 Gew.-% und besonders bevorzugt bis zu 0,5 Gew.-% Verunreinigungen enthalten kann, jeweils bezogen auf das Gesamtgewicht des eingesetzten 4,4'-Dichlordiphenylsulfons bzw. des eingesetzten 4,4'-Difluordiphenylsulfons. Die gegebenenfalls enthaltenen Verunreinigungen sind in den Gew-% Angaben in Bezug auf die Komponente (A1) mit enthalten.The 4,4'-dichlorodiphenyl sulfone and the 4,4'-difluorodiphenyl sulfone can be used as a pure substance or as a technical product, which can be up to 2 wt .-%, preferably up to 1 wt .-% and particularly preferably up to 0, Contain 5 wt .-% of impurities, each based on the total weight of the employed 4,4'-dichlorodiphenyl sulfone or of the used 4,4'-Difluordiphenylsulfons. The impurities which may be present are included in the percentage by weight with respect to component (A1).
In einer Ausführungsform enthält die Komponente (A1) mindestens 80 Gew.-%, bevorzugt mindestens 90 Gew.-% und besonders bevorzugt mindestens 98 Gew.-% mindestens einer Dihalogenverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon, bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG). Die Gewichtsprozentangaben in Bezug auf die Komponente (A1) beziehen sich dabei darüber hinaus auf die Summe des eingesetzten 4,4'-Dichlordiphenylsulfons und des eingesetzten 4,4'-Difluordiphenylsulfons.In one embodiment, component (A1) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 98% by weight of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone, based on the total weight of component (A1) in the reaction mixture (R G ). The percentages by weight with respect to component (A1) also refer to the sum of the 4,4'-dichlorodiphenylsulfone used and the 4,4'-difluorodiphenylsulfone used.
Die Komponente (A1) kann darüber hinaus andere, von 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon verschiedene, Dihalogenverbindungen enthalten. Die Komponente (A1) enthält maximal 50 Gew.-%, bevorzugt maximal 20 Gew.-%, besonders bevorzugt maximal 10 Gew.-% und insbesondere maximal 2 Gew.-% anderer Dihalogenverbindungen.The component (A1) may further contain other dihalogen compounds other than 4,4'-dichlorodiphenylsulfone and 4,4'-difluorodiphenylsulfone. Component (A1) contains not more than 50% by weight, preferably not more than 20% by weight, more preferably not more than 10% by weight and in particular not more than 2% by weight of other dihalogen compounds.
In einer besonders bevorzugten Ausführungsform enthält die Komponente (A1) mindestens 50 Gew.-%, bevorzugt mindestens 80 Gew.-%, besonders bevorzugt mindestens 90 Gew.-% und insbesondere mindestens 98 Gew.-% 4,4'-Dichlordiphenylsulfon.In a particularly preferred embodiment, component (A1) contains at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of 4,4'-dichlorodiphenyl sulfone.
Weiterhin ist es besonders bevorzugt, dass das Reaktionsgemisch (RG) neben den Dihalogenverbindungen der Komponente (A1) keine weiteren Dihalogenverbindungen enthält.Furthermore, it is particularly preferred that the reaction mixture (R G ) contains no further dihalogen compounds in addition to the dihalogen compounds of component (A1).
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren, bei dem das Reaktionsgemisch (RG) neben den Dihalogenverbindungen der Komponente (A1) keine weiteren Dihalogenverbindungen enthält.The present invention thus also provides a process in which the reaction mixture (R G ) contains no further dihalogen compounds in addition to the dihalogen compounds of component (A1).
In einer weiteren besonders bevorzugten Ausführungsform besteht die Komponente (A1) im Wesentlichen aus mindestens einer Dihalogenverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon. Unter "bestehend im Wesentlichen aus" wird vorliegend verstanden, dass die Komponente (A1) mehr als 99 Gew.%, bevorzugt mehr 99,5 Gew.-%, insbesondere bevorzugt mehr als 99,9 Gew.-% mindestens einer Dihalogenverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon enthält, jeweils bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG). Bei diesen Ausführungen ist 4,4'-Dichlordiphenylsulfon als Komponente (A1) besonders bevorzugt.In a further particularly preferred embodiment, component (A1) consists essentially of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone. By "consisting essentially of" is meant herein that the component (A1) more than 99 wt.%, Preferably more 99.5 wt .-%, particularly preferably more than 99.9 wt .-% of at least one dihalogen compound selected from the group consisting of 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, in each case based on the total weight of component (A1) in the reaction mixture (R G ). In these embodiments, 4,4'-dichlorodiphenyl sulfone is particularly preferred as component (A1).
In einer weiteren besonders bevorzugten Ausführungsform besteht Komponente (A1) im Wesentlichen aus 4,4'-Dichlordiphenylsulfon. In einer weiteren besonders bevorzugten Ausführungsform besteht Komponente (A1) aus 4,4'-Dichlordiphenylsulfon.In a further particularly preferred embodiment, component (A1) consists essentially of 4,4'-dichlorodiphenylsulfone. In a further particularly preferred embodiment, component (A1) consists of 4,4'-dichlorodiphenylsulfone.
Das Reaktionsgemisch (RG) enthält als Komponente (B1), die auch als Dihydroxykomponente bezeichnet wird, mindestens eine Dihydroxyverbindung. Unter "mindestens eine Dihydroxyverbindung" werden vorliegend genau eine Dihydroxyverbindung sowie Gemische aus zwei oder mehreren Dihydroxyverbindungen verstanden.The reaction mixture (R G ) contains as component (B1), which is also referred to as dihydroxy component, at least one dihydroxy compound. By "at least one dihydroxy compound" is meant in the present case exactly one dihydroxy compound and mixtures of two or more dihydroxy compounds.
Bei der Komponente (B1) kann es sich somit sowohl um eine einzelne Dihydroxyverbindung, als auch um Mischungen aus zwei oder mehreren Dihydroxyverbindungen handeln.The component (B1) may thus be both a single dihydroxy compound and mixtures of two or more dihydroxy compounds.
Es ist erfindungswesentlich, dass die Komponente (B1) mindestens 50 Gew.-% mindestens einer Dihydroxyverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dihydroxydiphenylsulfon, Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenon und Hydrochinon enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG). Die Gewichtsprozentangaben in Bezug auf die Komponente (B1) beziehen sich dabei darüber hinaus auf die Summe des eingesetzten 4,4'-Dihydroxydiphenylsulfons, Bisphenols A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenons und Hydrochinons. Unter den vorstehend genannten Dihydroxyverbindungen sind 4,4'-Dihydroxydiphenylsulfon und Bisphenol A bevorzugt, wobei Bisphenol A besonders bevorzugt ist.It is essential to the invention that component (B1) contains at least 50% by weight of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 4,4'-dihydroxybenzophenone and hydroquinone, based on the total weight of component (B1) in the reaction mixture (R G ). The percentages by weight with respect to component (B1) also relate to the sum of the 4,4'-dihydroxydiphenylsulfone used, bisphenol A (2,2-bis- (4-hydroxyphenyl) -propane), 4,4'- Dihydroxybenzophenone and hydroquinone. Among the above-mentioned dihydroxy compounds, 4,4'-dihydroxydiphenylsulfone and bisphenol A are preferable, with bisphenol A being particularly preferred.
Das 4,4'-Dihydroxydiphenylsulfon, das Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan), das 4,4'-Dihydroxybenzophenon und das Hydrochinon können dabei als Reinstoff oder als technisches Produkt eingesetzt werden, das bis zu 2 Gew.-%, bevorzugt bis zu 1 Gew.-% und besonders bevorzugt bis zu 0,5 Gew.-% Verunreinigungen enthalten kann, jeweils bezogen auf das Gesamtgewicht des eingesetzten 4,4'-Dihydroxydiphenylsulfons, des eingesetzten Bisphenols A (2,2-Bis-(4-hydroxyphenyl)-propan), des eingesetzten 4,4'-Dihydroxybenzophenons und des eingesetzten Hydrochinons. Die gegebenenfalls enthaltenen Verunreinigungen sind in den Gew-% Angaben in Bezug auf die Komponente (B1) mit enthalten.The 4,4'-dihydroxydiphenylsulfone, the bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), the 4,4'-dihydroxybenzophenone and the hydroquinone can be used as pure substance or as a technical product, the bis 2% by weight, preferably up to 1% by weight and more preferably up to 0.5% by weight of impurities, in each case based on the total weight of the 4,4'-dihydroxydiphenylsulfone used, of the bisphenol A used ( 2,2-bis (4-hydroxyphenyl) propane), the 4,4'-dihydroxybenzophenone used and the hydroquinone used. The impurities which may be present are included in the percentage by weight with respect to component (B1).
In einer Ausführungsform enthält die Komponente (B1) mindestens 80 Gew.-%, bevorzugt mindestens 90 Gew.-% und besonders bevorzugt mindestens 98 Gew.-% mindestens einer Dihydroxyverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dihydroxydiphenylsulfon, Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenon und Hydrochinon, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG). Die Gewichtsprozentangaben in Bezug auf die Komponente (B1) beziehen sich dabei darüber hinaus auf die Summe des eingesetzten 4,4'-Dihydroxydiphenylsulfons, Bisphenols A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenons und Hydrochinons.In one embodiment, component (B1) contains at least 80% by weight, preferably at least 90% by weight and particularly preferably at least 98% by weight of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A. (2,2-bis (4-hydroxyphenyl) propane), 4,4'-dihydroxybenzophenone and hydroquinone, based on the total weight of component (B1) in the reaction mixture (R G ). The percentages by weight with respect to component (B1) also relate to the sum of the 4,4'-dihydroxydiphenylsulfone used, bisphenol A (2,2-bis- (4-hydroxyphenyl) -propane), 4,4'- Dihydroxybenzophenone and hydroquinone.
Die Komponente (B1) kann darüber hinaus andere, von 4,4'-Dihydroxydiphenylsulfon, Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenon und Hydrochinon verschiedene, Dihydroxyverbindungen enthalten. Die Komponente (B1) enthält maximal 50 Gew.-%, bevorzugt maximal 20 Gew.-%, besonders bevorzugt maximal 10 Gew.-% und insbesondere maximal 2 Gew.-% anderer Dihydroxyverbindungen.The component (B1) may further contain other dihydroxy compounds other than 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 4,4'-dihydroxybenzophenone and hydroquinone. The component (B1) contains not more than 50% by weight, preferably not more than 20% by weight, more preferably not more than 10% by weight and in particular not more than 2% by weight of other dihydroxy compounds.
Als andere Dihydroxyverbindungen können beispielsweise alle bekannten Verbindungen eingesetzt werden, die zwei phenolische Hydroxygruppen aufweisen. Unter "phenolische Hydroxygruppe" wird erfindungsgemäß eine Hydroxygruppe (-OH) verstanden, die an ein aromatisches System gebunden ist. Geeignete andere Dihydroxyverbindungen sind beispielsweise Resorcin (1,3-Dihydroxybenzol), Dihydroxynaphthaline, Bisphenol TMC (1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan), Bisphenol AF (2,2-Bis(4-hydroxyphenyl)hexafluorpropan), 1,1-Bis(4-hydroxyphenyl)-3,3-dimethyl-cyclopentan und/oder 4,4`-Dihydroxybiphenyl.As other dihydroxy compounds, it is possible to use, for example, all known compounds which have two phenolic hydroxyl groups. By "phenolic hydroxy group" is meant according to the invention a hydroxy group (-OH) which is bonded to an aromatic system. Suitable other dihydroxy compounds are, for example, resorcinol (1,3-dihydroxybenzene), dihydroxynaphthalenes, bisphenol TMC (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane), bisphenol AF (2,2-bis (4-bis) hydroxyphenyl) hexafluoropropane), 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclopentane and / or 4,4'-dihydroxybiphenyl.
In einer besonders bevorzugten Ausführungsform enthält die Komponente (B1) mindestens 50 Gew.-%, bevorzugt mindestens 80 Gew.-%, besonders bevorzugt mindestens 90 Gew.-% und insbesondere mindestens 98 Gew.-% Bisphenol A.In a particularly preferred embodiment, component (B1) contains at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of bisphenol A.
In einer besonders bevorzugten Ausführungsform enthält die Komponente (B1) mindestens 50 Gew.-%, bevorzugt mindestens 80 Gew.-%, besonders bevorzugt mindestens 90 Gew.-% und insbesondere mindestens 98 Gew.-% 4,4'-Dihydroxydiphenylsulfon.In a particularly preferred embodiment, component (B1) contains at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight and in particular at least 98% by weight of 4,4'-dihydroxydiphenylsulfone.
Weiterhin ist es besonders bevorzugt, dass das Reaktionsgemisch (RG) neben den Dihalogenverbindungen der Komponente (B1) keine weiteren Dihydroxyverbindungen enthält.Furthermore, it is particularly preferred that the reaction mixture (R G ) contains no further dihydroxy compounds in addition to the dihalogen compounds of component (B1).
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren, bei dem das Reaktionsgemisch (RG) neben den Dihalogenverbindungen der Komponente (B1) keine weiteren Dihydroxyverbindungen enthält.The present invention thus also provides a process in which the reaction mixture (R G ) contains no further dihydroxy compounds in addition to the dihalogen compounds of component (B1).
In einer weiteren besonders bevorzugten Ausführungsform besteht die Komponente (B1) im Wesentlichen aus mindestens einer Dihydroxyverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dihydroxydiphenylsulfon, Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenon und Hydrochinon. Unter "bestehend im Wesentlichen aus" wird vorliegend verstanden, dass die Komponente (B1) mehr als 99 Gew.%, bevorzugt mehr 99,5 Gew.-%, insbesondere bevorzugt mehr als 99,9 Gew.-% mindestens einer Dihydroxyverbindung ausgewählt aus der Gruppe bestehend aus 4,4'-Dihydroxydiphenylsulfon, Bisphenol A (2,2-Bis-(4-hydroxyphenyl)-propan), 4,4'-Dihydroxybenzophenon und Hydrochinon enthält, jeweils bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG). Bei diesen Ausführungen ist Bisphenol A und 4,4'-Dihydroxydiphenlysulfon als Komponente (B1) besonders bevorzugt, wobei Bisphenol A am Meisten bevorzugt ist.In a further particularly preferred embodiment, component (B1) consists essentially of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) -propane), 4 , 4'-Dihydroxybenzophenone and hydroquinone. By "consisting essentially of" is meant herein that the component (B1) more than 99 wt.%, Preferably more 99.5 wt .-%, particularly preferably more than 99.9 wt .-% of at least one dihydroxy compound selected from the group consisting of 4,4'-dihydroxydiphenylsulfone, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), 4,4'-dihydroxybenzophenone and hydroquinone, each based on the total weight of component (B1) in the reaction mixture (R G ). In these embodiments, bisphenol A and 4,4'-dihydroxydiphenylsulfone are particularly preferred as component (B1), with bisphenol A being most preferred.
In einer weiteren besonders bevorzugten Ausführungsform besteht Komponente (B1) im Wesentlichen aus Bisphenol A. In einer weiteren besonders bevorzugten Ausführungsform besteht Komponente (B1) aus Bisphenol A.In a further particularly preferred embodiment, component (B1) consists essentially of bisphenol A. In a further particularly preferred embodiment, component (B1) consists of bisphenol A.
Da das Reaktionsgemisch (RG) als Komponente (C) Kaliumkarbonat enthält, können die Hydroxygruppen der als Komponente (B1) eingesetzten Dihydroxyverbindungen im Reaktionsgemisch (RG) teilweise in deprotonierter Form vorliegen.Since the reaction mixture (R G ) as component (C) contains potassium carbonate, the hydroxy groups of the dihydroxy compounds used as component (B1) in the reaction mixture (R G ) may be partially present in deprotonated form.
In einer Ausführungsform der vorliegenden Erfindung enthält das Reaktionsgemisch (RG) kein 4,4'-Dihydroxybiphenyl.In one embodiment of the present invention, the reaction mixture (R G ) does not contain 4,4'-dihydroxybiphenyl.
Das Reaktionsgemisch (RG) enthält als Komponente (C), die auch als Karbonatkomponente bezeichnet wird, Kaliumkarbonat. Das Kaliumkarbonat ist bevorzugt wasserfrei.The reaction mixture (R G ) contains as component (C), which is also referred to as carbonate component, potassium carbonate. The potassium carbonate is preferably anhydrous.
Es ist erfindungswesentlich, dass die Komponente (C) mindestens 50 Gew.-% Kaliumkarbonat mit einer volumengemittelten Partikelgröße von < 25 µm enthält, bezogen auf das Gesamtgewicht der Komponente (C) im Reaktionsgemisch (RG).It is essential to the invention that component (C) contains at least 50% by weight of potassium carbonate having a volume-average particle size of <25 μm, based on the total weight of component (C) in the reaction mixture (R G ).
Das Kaliumkarbonat kann als Reinstoff oder als technisches Produkt eingesetzt werden, das bis zu 2 Gew.-%, bevorzugt bis zu 1 Gew.-% und besonders bevorzugt bis zu 0,5 Gew.-% Verunreinigungen enthalten kann, jeweils bezogen auf das Gesamtgewicht des eingesetzten Kaliumkarbonats. Die gegebenenfalls im Kaliumkarbonat enthaltenen Verunreinigungen sind in den Gew-% Angaben in Bezug auf die Komponente (C) mit enthalten.The potassium carbonate can be used as a pure substance or as a technical product, which may contain up to 2 wt .-%, preferably up to 1 wt .-% and particularly preferably up to 0.5 wt .-% impurities, each based on the total weight of the potassium carbonate used. The impurities which may be present in the potassium carbonate are included in the percentage by weight with respect to component (C).
In einer Ausführungsform enthält die Komponente (C) mindestens 80 Gew.-%, bevorzugt mindestens 90 Gew.-% und besonders bevorzugt mindestens 98 Gew.-% Kaliumkarbonat mit einer volumengemittelten Partikelgröße von < 25 µm, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG).In one embodiment, component (C) contains at least 80 wt .-%, preferably at least 90 wt .-% and particularly preferably at least 98 wt .-% potassium carbonate having a volume-average particle size of <25 microns, based on the total weight of the component (B1 ) in the reaction mixture (R G ).
Die Komponente (C) kann darüber hinaus andere, von Kaliumkarbonat verschiedene, Karbonatverbindungen enthalten. Die Komponente (C) enthält maximal 50 Gew.-%, bevorzugt maximal 20 Gew.-%, besonders bevorzugt maximal 10 Gew.-% und insbesondere maximal 2 Gew.-% anderer Karbonatverbindungen.The component (C) may further contain other carbonate compounds other than potassium carbonate. Component (C) contains not more than 50% by weight, preferably not more than 20% by weight, more preferably not more than 10% by weight and in particular not more than 2% by weight of other carbonate compounds.
Als andere Karbonatverbindungen können beispielsweise Ammoniumkarbonat, Ammoniumhydrogenkarbonat, Lithiumkarbonat, Lithiumhydrogenkarbonat, Natriumkarbonat, Natriumhydrogenkarbonat, Kaliumhydrogenkarbonat sowie Erdalkalikarbonate und Erdalkalihydrogenkarbonate eingesetzt werden.As other carbonate compounds, for example, ammonium carbonate, ammonium bicarbonate, lithium carbonate, lithium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium bicarbonate and alkaline earth carbonates and Erdalkalihydrogenkarbonate can be used.
In einer bevorzugten Ausführungsform besteht Komponente (C) im Wesentlichen aus Kaliumkarbonat. Unter "bestehend im Wesentlichen aus" wird vorliegend verstanden, dass die Komponente (C) mehr als 99 Gew.-%, bevorzugt mehr als 99,5 Gew.-%, insbesondere bevorzugt mehr als 99,9 Gew.-% Kaliumkarbonat enthält, jeweils bezogen auf das Gesamtgewicht der Komponente (C) im Reaktionsgemisch (RG).In a preferred embodiment, component (C) consists essentially of potassium carbonate. By "consisting essentially of" is meant herein that component (C) contains more than 99% by weight, preferably more than 99.5% by weight, particularly preferably more than 99.9% by weight of potassium carbonate, in each case based on the total weight of component (C) in the reaction mixture (R G ).
In einer besonders bevorzugten Ausführungsform besteht Komponente (C) aus Kaliumkarbonat.In a particularly preferred embodiment, component (C) consists of potassium carbonate.
Weiterhin ist es besonders bevorzugt, dass das Reaktionsgemisch (RG) neben der Komponente (C) keine weiteren Karbonatverbindungen, insbesondere kein Natriumkarbonat oder Natriumhydrogenkarbonat enthält. In einer bevorzugten Ausführungsform enthält das Reaktionsgemisch (RG) kein Natriumkarbonat und kein Natriumhydrogenkarbonat.Furthermore, it is particularly preferred that the reaction mixture (R G ) in addition to the component (C) contains no further carbonate compounds, in particular no sodium carbonate or sodium bicarbonate. In a preferred embodiment, the reaction mixture (R G ) contains no sodium carbonate and no sodium bicarbonate.
Als Kaliumkarbonat bevorzugt ist Kaliumkarbonat mit einer volumengewichteten mittleren Teilchengröße (D[4,3]) von weniger als 25 µm. Die volumengewichtete mittlere Teilchengröße (D[4,3]) des Kaliumkarbonats wird dabei bestimmt mit einem Partikelgrößenmessgerät in einer Suspension des Kaliumkarbonats in einer Mischung aus Chlorbenzol und Sulfolan. Die volumengemittelte Partikelgröße (D[4,3]) kann beispielsweise mit einem Mastersizer 2000 der Firma Malvern an einer Suspension der Partikel in Chlorbenzol/Sulfolan (60/40) bestimmt werden.Potassium carbonate is preferred as the potassium carbonate with a volume-weighted average particle size (D [4,3]) of less than 25 microns. The volume-weighted average particle size (D [4,3]) of the potassium carbonate is determined using a particle size measuring device in a suspension of the potassium carbonate in a mixture of chlorobenzene and sulfolane. The volume-average particle size (D [4,3]) can be determined, for example, with a Mastersizer 2000 from Malvern on a suspension of the particles in chlorobenzene / sulfolane (60/40).
Besonders bevorzugt ist Kaliumkarbonat mit einer volumengemittelten Partikelgröße (D[4,3]) kleiner 15 µm. Besonders bevorzugtes Kaliumkarbonat weist eine volumengemittelte Partikelgröße (D[4,3]) im Bereich von 20 nm bis <25 µm auf. Insbesondere bevorzugtes Kaliumkarbonat weist eine volumengemittelte Partikelgröße im Bereich von 20 nm bis 15 µm auf.Particularly preferred is potassium carbonate having a volume-average particle size (D [4,3]) less than 15 microns. Particularly preferred potassium carbonate has a volume-average particle size (D [4,3]) in the range from 20 nm to <25 μm. In particular, preferred potassium carbonate has a volume-average particle size in the range of 20 nm to 15 microns.
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren, bei dem das Kaliumcarbonat eine volumengemittelte Partikelgröße im Bereich von 20 nm bis < 25 µm, bevorzugt im Bereich von 20 nm bis 15 µm, aufweist.The present invention thus also provides a process in which the potassium carbonate has a volume-average particle size in the range from 20 nm to <25 μm, preferably in the range from 20 nm to 15 μm.
Gegebenenfalls enthält das Reaktionsgemisch (RG) als Komponente (D) mindestens ein aprotisches polares Lösungsmittel. Unter "mindestens ein aprotisches polares Lösungsmittel" werden erfindungsgemäß genau ein aprotisches polares Lösungsmittel sowie Gemische aus zwei oder mehreren aprotischen polaren Lösungsmitteln verstanden.If appropriate, the reaction mixture (R G ) contains at least one aprotic polar solvent as component (D). Under "at least one aprotic polar Solvent "are understood according to the invention exactly an aprotic polar solvent and mixtures of two or more aprotic polar solvents.
Als aprotisches polares Lösungsmittel sind beispielsweise Anisol, Dimethylformamid, Dimethylsulfoxid, Sulfolan, N-Methyl-2-Pyrrolidon, N-Ethyl-2-Pyrrolidon sowie Mischungen dieser Lösungsmittel geeignet.As aprotic polar solvent, for example, anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and mixtures of these solvents are suitable.
Als aprotisches polares Lösungsmittel sind N-Methyl-2-Pyrrolidon, N-Ethyl-2-Pyrrolidon sowie Mischungen dieser Lösungsmittel bevorzugt. Besonders bevorzugt als aprotisches polares Lösungsmittel ist N-Methyl-2-Pyrrolidon.As the aprotic polar solvent, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and mixtures of these solvents are preferred. Particularly preferred as the aprotic polar solvent is N-methyl-2-pyrrolidone.
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren, bei dem das Reaktionsgemisch (RG) als Komponente (D) mindestens ein aprotisches polares Lösungsmittel ausgewählt aus der Gruppe bestehend aus Anisol, Dimethylformamid, Dimethylsulfoxid, Sulfolan, N-Methyl-2-Pyrrolidon und N-Ethyl-2-Pyrrolidon enthält.The present invention thus also provides a process in which the reaction mixture (R G ) as component (D) at least one aprotic polar solvent selected from the group consisting of anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and Contains N-ethyl-2-pyrrolidone.
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren, bei dem das Reaktionsgemisch (RG) als Komponente (D) N-Methyl-2-Pyrrolidon enthält.The present invention thus also provides a process in which the reaction mixture (R G ) contains N-methyl-2-pyrrolidone as component (D).
In einer bevorzugten Ausführungsform enthält Komponente (D) mindestens 50 Gew.-% mindestens eines Lösungsmittels ausgewählt aus der Gruppe bestehend aus N-Methyl-2-Pyrrolidon und N-Ethyl-2-Pyrrolidon, bezogen auf das Gesamtgewicht der Komponente (D) im Reaktionsgemisch (RG). Als Komponente (D) ist N-Methyl-2-Pyrrolidon besonders bevorzugt.In a preferred embodiment, component (D) contains at least 50 wt .-% of at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, based on the total weight of component (D) in Reaction mixture (R G ). As component (D), N-methyl-2-pyrrolidone is particularly preferred.
In einer weiteren Ausführungsform besteht Komponente (D) im Wesentlichen aus mindestens einem Lösungsmittels ausgewählt aus der Gruppe bestehend aus N-Methyl-2-Pyrrolidon und N-Ethyl-2-Pyrrolidon. Unter "bestehend im Wesentlichen aus" wird vorliegend verstanden, dass die Komponente (D) mehr als 99 Gew.-%, insbesondere bevorzugt mehr als 99,5 Gew.-%, insbesondere bevorzugt mehr als 99,9 Gew.-% mindestens eines aprotischen polaren Lösungsmittels ausgewählt aus der Gruppe bestehend aus N-Methyl-2-Pyrrolidon und N-Ethyl-2-Pyrrolidon enthält, jeweils bezogen auf das Gesamtgewicht der Komponente (D) im Reaktionsgemisch (RG), wobei N-Methyl-2-Pyrrolidon bevorzugt ist.In a further embodiment, component (D) consists essentially of at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone. By "consisting essentially of" is meant herein that the component (D) more than 99 wt .-%, more preferably more than 99.5 wt .-%, particularly preferably more than 99.9 wt .-% of at least one aprotic polar solvent selected from the group consisting of N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, in each case based on the total weight of component (D) in the reaction mixture (R G ), where N-methyl-2- Pyrrolidone is preferred.
In einer bevorzugten Ausführungsform besteht Komponente (D) aus N-Methyl-2-Pyrrolidon. N-Methyl-2-Pyrrolidon wird auch als NMP oder N-Methylpyrrolidon bezeichnet.In a preferred embodiment, component (D) consists of N-methyl-2-pyrrolidone. N-methyl-2-pyrrolidone is also referred to as NMP or N-methylpyrrolidone.
In einer weiteren bevorzugten Ausführungsform enthält das Reaktionsgemisch neben den aprotischen polaren Lösungsmitteln der Komponente (D) keine weiteren aprotischen polaren Lösungsmittel.In a further preferred embodiment, the reaction mixture contains, in addition to the aprotic polar solvents of component (D), no further aprotic polar solvents.
Besonders bevorzugt ist ein Reaktionsgemisch (RG), in dem
die Komponente (A1) mindestens 50 Gew.-%, bevorzugt mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% 4,4'-Dichlordiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG),
die Komponente (B1) mindestens 50 Gew.-%, bevorzugt mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% 4,4'-Dihydroxydiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG),
die Komponente (C) im Wesentlichen aus Kaliumcarbonat mit einer volumengemittelten Partikelgröße von < 25 µm besteht und
die Komponente (D) im Wesentlichen aus N-Methylpyrrolidon besteht.Particularly preferred is a reaction mixture (R G), in which
the component (A1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1) in the reaction mixture (R G )
component (B1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dihydroxydiphenylsulfone, based on the total weight of component (B1) in the reaction mixture (R G )
the component (C) consists essentially of potassium carbonate having a volume-average particle size of <25 microns, and
the component (D) consists essentially of N-methylpyrrolidone.
Weiterhin besonders bevorzugt ist ein Reaktionsgemisch (RG), in dem
die Komponente (A1) mindestens 50 Gew.-%, bevorzugt mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% 4,4'-Dichlordiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (A1) im Reaktionsgemisch (RG),
die Komponente (B1) mindestens 50 Gew.-%, bevorzugt mindestens 90 Gew.-%, besonders bevorzugt mindestens 95 Gew.-% Bisphenol A enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG),
die Komponente (C) im Wesentlichen aus Kaliumcarbonat mit einer volumengemittelten Partikelgröße von < 25 µm besteht und
die Komponente (D) im Wesentlichen aus N-Methylpyrrolidon besteht.Also particularly preferred is a reaction mixture (R G ) in which
the component (A1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1) in the reaction mixture (R G )
component (B1) contains at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of bisphenol A, based on the total weight of component (B1) in the reaction mixture (R G ),
the component (C) consists essentially of potassium carbonate having a volume-average particle size of <25 microns, and
the component (D) consists essentially of N-methylpyrrolidone.
Das Verhältnis der Komponenten (A1) und (B1) im Reaktionsgemisch (RG) kann in weiten Bereichen variieren. Bevorzugt liegt das molare Verhältnis der Komponente (B1) zu (A1) im Bereich von 0,95 bis 1,05 zu 1, bevorzugt im Bereich von 0,97 bis 1,03 zu 1.The ratio of components (A1) and (B1) in the reaction mixture (R G ) can vary within wide limits. The molar ratio of component (B1) to (A1) is preferably in the range from 0.95 to 1.05 to 1, preferably in the range from 0.97 to 1.03 to 1.
Zur Herstellung des erfindungsgemäßen Polyarylenethersulfon-Polymers wird das Reaktionsgemisch (RG) unter Bedingungen der sogenannten Karbonatmethode zur Reaktion gebracht. Die Umsetzung (Polykondensationsreaktion) erfolgt dabei im Allgemeinen bei Temperaturen im Bereich von 80 bis 250 °C, bevorzugt im Bereich von 100 bis 220 °C, wobei die Obergrenze der Temperatur durch den Siedepunkt des aprotischen polaren Lösungsmittels (Komponente D) bei Normaldruck (1013,25 mbar) bestimmt wird. Die Umsetzung wird im Allgemeinen bei Normaldruck durchgeführt. Die Umsetzung erfolgt vorzugsweise in einem Zeitintervall von 2 bis 12 Stunden, insbesondere im Bereich von 3 bis 10 Stunden.To prepare the polyarylene ether sulfone polymer according to the invention, the reaction mixture (R G ) is reacted under conditions of the so-called carbonate method. The reaction (polycondensation reaction) is generally carried out at temperatures in the range of 80 to 250 ° C, preferably in the range of 100 to 220 ° C, wherein the upper limit of the temperature by the boiling point of the aprotic polar solvent (component D) at atmospheric pressure (1013 , 25 mbar). The reaction is generally carried out at atmospheric pressure. The reaction is preferably carried out in a time interval of 2 to 12 hours, in particular in the range of 3 to 10 hours.
Die Isolierung des erfindungsgemäß erhaltenen Polyarylenethersulfon-Polymers kann beispielsweise durch Fällung der Polymerlösung in Wasser oder Gemischen von Wasser mit weiteren Lösungsmitteln erfolgen. Das ausgefällte Polyarylenethersulfon-Polymer kann anschließend mit Wasser extrahiert und danach getrocknet werden. In einer Ausführungsform der Erfindung kann die Fällung auch in einem sauren Medium vorgenommen werden. Geeignete Säuren sind beispielsweise organische oder anorganische Säuren, beispielsweise Carbonsäuren wie Essigsäure, Propionsäure, Bernsteinsäure oder Zitronensäure sowie Mineralsäuren wie beispielsweise Salzsäure, Schwefelsäure oder Phosphorsäure.The isolation of the polyarylene ether sulfone polymer obtained according to the invention can be carried out, for example, by precipitation of the polymer solution in water or mixtures of water with further solvents. The precipitated polyarylene ether sulfone polymer can then be extracted with water and then dried. In one embodiment of the invention, the precipitation can also be carried out in an acidic medium. Suitable acids are, for example, organic or inorganic acids, for example carboxylic acids such as acetic acid, propionic acid, succinic acid or citric acid, and mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid.
Durch das erfindungsgemäße Verfahren werden Polyarylenethersulfon-Polymere mit niedrigen Polydispersitäten (Q) erhalten.The process according to the invention gives polyarylene ether sulfone polymers having low polydispersities (Q).
Gegenstand der vorliegenden Erfindung ist somit auch ein Polyarylenethersulfon-Polymer, das nach dem erfindungsgemäßen Verfahren erhältlich ist.The present invention thus also provides a polyarylene ether sulfone polymer obtainable by the process according to the invention.
Das Polyarylenethersulfon-Polymer weist im Allgemeinen eine Polydispersität (Q) von ≤ 4, bevorzugt von ≤ 3,5 auf.The polyarylene ether sulfone polymer generally has a polydispersity (Q) of ≦ 4, preferably ≦ 3.5.
Die Polydispersität (Q) ist definiert als Quotient aus dem gewichtsmittleren Molekulargewicht (Mw) und dem zahlenmittleren Molekulargewicht (Mn). In einer bevorzugten Ausführungsform liegt die Polydispersität (Q) des Polyarylenethersulfon-Polymers im Bereich von 2,0 bis ≤ 4, bevorzugt im Bereich von 2,0 bis ≤ 3,5.The polydispersity (Q) is defined as the quotient of the weight-average molecular weight (Mw) and the number-average molecular weight (M n ). In a preferred embodiment, the polydispersity (Q) of the polyarylene ether sulfone polymer is in the range of 2.0 to ≦ 4, preferably in the range of 2.0 to ≦ 3.5.
Das gewichtsmittlere Molekulargewicht (Mw) und das zahlenmittlere Molekulargewicht (Mn) werden mittels Gelpermeationschromatographie gemessen.The weight-average molecular weight (M w ) and the number-average molecular weight (M n ) are measured by gel permeation chromatography.
Die Polydispersität (Q) und die mittleren Molekulargewichte des Polyarylenethersulfon-Polymers wurden mittels Gelpermeationschromatographie (GPC) gemessen. Als Lösungsmittel wurde Dimethylacetamid (DMAc) verwendet und gegen engverteiltes Polymethylmethacrylat als Standard gemessen.The polydispersity (Q) and the average molecular weights of the polyarylene ether sulfone polymer were measured by gel permeation chromatography (GPC). As the solvent, dimethylacetamide (DMAc) was used and measured against narrow-divided polymethyl methacrylate as a standard.
Geeignete Herstellungsverfahren, für die vorgenannten Polyarylenethersulfon-Polymeren, sind dem Fachmann an sich bekannt und beispielsweise in
Bevorzugte Polyarylenethersulfon-Polymere sind solche, die mindestens eine der folgenden Bausteine la bis Ib als wiederkehrende Struktureinheiten enthalten:
Es ist außerdem besonders bevorzugt, wenn das Polyarylenethersulfon-Polymer im Wesentlichen aus mindestens einer Sorte Bausteine ausgewählt aus der Gruppe la und Ib aufgebaut sind.It is also particularly preferred if the polyarylene ether sulfone polymer is essentially composed of at least one kind of building blocks selected from the group Ia and Ib.
Besonders bevorzugt sind Polyarylenethersulfon-Polymere, die aus Wiederholungseinheiten der Formel la aufgebaut sind. Diese Polyarylenethersulfon-Polymere werden auch als Polysulfon (PSU) bezeichnet.Particularly preferred are polyarylene ether sulfone polymers which are composed of repeating units of the formula Ia. These polyarylene ether sulfone polymers are also referred to as polysulfone (PSU).
Weiterhin besonders bevorzugt sind Polyarylenethersulfon-Polymere, die aus Wiederholungseinheiten der Formel Ib aufgebaut sind. Diese Polyarylenethersulfon-Polymere werden auch als Polyethersulfon (PESU) bezeichnet.Also particularly preferred are polyarylene ether sulfone polymers which are composed of repeating units of the formula Ib. These polyarylene ether sulfone polymers are also referred to as polyethersulfone (PESU).
Abkürzungen wie PESU und PSU entsprechen im Rahmen der vorliegenden Erfindung der DIN EN ISO 1043-1 (Kunststoffe - Kennbuchstaben und Kurzzeichen - Teil 1: Basis-Polymere und ihre besonderen Eigenschaften (ISO 1043-1:2001); Deutsche Fassung EN ISO 1043-1:2002).Abbreviations such as PESU and PSU correspond in the context of the present invention to DIN EN ISO 1043-1 (Plastics - Coding Letters and Abbreviations - Part 1: Basic Polymers and their Special Properties (ISO 1043-1: 2001); 1: 2002).
Weiterhin besonders bevorzugt sind Copolymere oder Blockcopolymere, die aus Wiederholungseinheiten der Formeln la und Ib aufgebaut sind.Particular preference is furthermore given to copolymers or block copolymers which are built up from repeat units of the formulas Ia and Ib.
Das nach dem erfindungsgemäßen Verfahren erhältliche Polyarylenethersulfon-Polymer weist im Allgemeinen gewichtsmittlere Molekulargewichte (Mw) von 10 000 bis 150 000 g/mol, bevorzugt im Bereich von 15 000 bis 120 000 g/mol, besonders bevorzugt im Bereich von 18 000 bis 100 000 g/mol auf. Die gewichtsmittleren Molekulargewichte (Mw) werden mittels Gelpermeationschromatographie (GPC) gemessen. Die Messung erfolgt dabei wie vorstehend beschrieben.The polyarylene ether sulfone polymer obtainable by the process according to the invention generally has weight-average molecular weights (M w ) of from 10 000 to 150 000 g / mol, preferably in the range from 15 000 to 120 000 g / mol, particularly preferably in the range from 18 000 to 100 000 g / mol. The weight average Molecular weights (Mw) are measured by gel permeation chromatography (GPC). The measurement is carried out as described above.
Die Polyarylenethersulfon-Polymere weisen in Abhängigkeit von den Reaktionsbedingungen und den molaren Verhältnissen der Komponenten (A1) und (B1) im Allgemeinen entweder Halogenendgruppen, insbesondere Chlorendgruppen, oder veretherte Endgruppen, insbesondere Alkyletherendgruppen, auf. Die veretherten Endgruppen sind durch Umsetzung der OH- bzw. Phenolat-Endgruppen mit geeigneten Veretherungsmitteln erhältlich.Depending on the reaction conditions and the molar ratios of components (A1) and (B1), the polyarylene ether sulfone polymers generally have either halogen end groups, in particular chlorine end groups, or etherified end groups, in particular alkyl ether end groups. The etherified end groups can be obtained by reacting the OH or phenolate end groups with suitable etherifying agents.
Geeignete Veretherungsmittel sind beispielsweise monofunktionelles Alkyl- oder Arylhalogenid, beispielsweise C1-C6-Alkylchlorid, -bromid oder -iodid, bevorzugt Methylchlorid, oder Benzylchlorid, -bromid oder -iodid oder Mischungen davon. Bevorzugte Endgruppen des erfindungsgemäßen Polyarylenethersulfon-Polymere sind Halogenendgruppen, insbesondere Chlor, sowie Alkoxyendgruppen, insbesondere Methoxy, Aryloxyendgruppen, insbesondere Phenoxy, oder Benzyloxy.Suitable etherifying agents are, for example, monofunctional alkyl or aryl halide, for example C 1 -C 6 -alkyl chloride, bromide or iodide, preferably methyl chloride, or benzyl chloride, bromide or iodide or mixtures thereof. Preferred end groups of the polyarylene ether sulfone polymers according to the invention are halogen end groups, in particular chlorine, and alkoxy end groups, in particular methoxy, aryloxy end groups, in particular phenoxy, or benzyloxy.
Aufgrund der guten Hydrolysebeständigkeit, begründet in der geringen Hydrophilie, werden Polyarylenethersulfon-Polymere, besonders lineare Polyarylenethersulfon-Polymere, seit vielen Jahren als Membranmaterialien verwendet. So beschreiben zum Beispiel
Die
In einer bevorzugten Ausführungsform werden Polyarylenethersulfon-Polymere im die erfindungsgemäßen Verfahren zur Herstellung der Polyarylenethersulfon-Polymere nicht sulfoniert. In einer weiteren bevorzugten Ausführungsform weisen die nach dem erfindungsgemäßen Verfahren erhältlichen Polyarylenethersulfon-Polymere somit keine freien Sulfonsäuregruppen auf.In a preferred embodiment, polyarylene ether sulfone polymers are not sulfonated in the inventive processes for preparing the polyarylene ether sulfone polymers. In a further preferred embodiment, the according to the According to the invention available polyarylene ether sulfone polymers thus no free sulfonic acid groups.
Die Herstellung von Hohlfasermembranen für Dialysemodule stellt besondere Anforderungen an das zur Herstellung verwendeter Polymermaterial. Hierbei sind insbesondere die Trennleistung und die Ausschlussgrenze betreffend das Molekulargewicht und somit die Fähigkeit, bestimmte Toxine bei der Dialyse herauszufiltern, sowie eine hohe Beständigkeit unter den Bedingungen der Sterilisation und eine hohe Beständigkeit der Eigenschaften der Membran über einen langen Zeitraum zu nennen.The production of hollow fiber membranes for dialysis modules makes special demands on the polymer material used for the production. In particular, the separation efficiency and the exclusion limit regarding the molecular weight, and thus the ability to filter out certain toxins in dialysis, as well as a high resistance under the conditions of sterilization and a high durability of the properties of the membrane over a long period of time.
Beispielsweise beschreibt die
Die mechanischen Eigenschaften im Dauergebrauch, die Verarbeitbarkeit bei der Herstellung und die Trennleistung, insbesondere die Ausschlussgrenze (definiert als Molekulargewicht, oberhalb dessen eine Abtrennung erfolgt) sind bei den in bekannten Dialysemembranen verwendeten Materialien jedoch nicht in allen Fällen zufriedenstellend.However, the mechanical properties in continuous use, the processability in the production and the separation performance, in particular the exclusion limit (defined as the molecular weight above which separation takes place) are not always satisfactory in the materials used in known dialysis membranes.
Die Herstellung von Membranen unter Verwendung des nach dem erfindungsgemäßen Verfahren erhältlichen Polyarylenethersulfon-Polymers kann durch Anwendung dem Fachmann an sich bekannter Schritte oder Verfahren erfolgen.The preparation of membranes using the polyarylene ether sulfone polymer obtainable by the process according to the invention can be carried out by using steps or processes known per se to those skilled in the art.
Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung einer Membran umfassend die folgenden Schritte:
- (i) Bereitstellen einer Lösung enthaltend das erfindungsgemäße Polyarylenethersulfon-Polymer und mindestens ein aprotisches polares Lösungsmittel und
- (ii) Trennung des erfindungsgemäßen Polyarylenethersulfon-Polymers vom aprotischen polaren Lösungsmittel unter Ausbildung einer Membran.
- (I) providing a solution containing the inventive polyarylene ether sulfone polymer and at least one aprotic polar solvent and
- (ii) separating the polyarylene ether sulfone polymer of the invention from the aprotic polar solvent to form a membrane.
Um die Hydrophilie der Membran zu steigern, kann der in Verfahrensschritt (i) bereitgestellten Lösung mindestens ein hydrophiles Polymer zugegeben werden. Ein geeignetes hydrophiles Polymer ist beispielsweise Polyvinylpyrrolidon mit einem gewichtsmittleren Molekulargewicht (Mw) im Bereich von 10 000 bis 2 000 000 g/mol, bevorzugt im Bereich von 200 000 bis 1 600 000 g/mol.In order to increase the hydrophilicity of the membrane, at least one hydrophilic polymer may be added to the solution provided in step (i). A suitable hydrophilic polymer is, for example, polyvinylpyrrolidone having a weight average molecular weight (M w ) in the range of 10,000 to 2,000,000 g / mol, preferably in the range of 200,000 to 1,600,000 g / mol.
Gegenstand der vorliegenden Erfindung ist auch ein Verfahren zur Herstellung einer Membran umfassend die folgenden Schritte:
- (i) Bereitstellen einer Lösung enthaltend das erfindungsgemäße Polyarylenethersulfon-Polymer, mindestens ein hydrophiles Polymer und mindestens ein aprotisches polares Lösungsmittel und
- (ii) Trennung der Mischung aus dem erfindungsgemäßen Polyarylenethersulfon-Polymers und dem hydrophilen Polymer vom aprotischen polaren Lösungsmittel unter Ausbildung einer Membran.
- (I) providing a solution containing the inventive polyarylene ether sulfone polymer, at least one hydrophilic polymer and at least one aprotic polar solvent and
- (ii) separating the mixture of the polyarylene ether sulfone polymer of the present invention and the hydrophilic polymer from the aprotic polar solvent to form a membrane.
In Schritt (i) erfolgt somit die Bereitstellung einer Lösung des Polyarylenethersulfon-Polymers und gegebenenfalls des hydrophilen Polymers in einem aprotischen polaren Lösungsmittel. Als aprotische polare Lösungsmittel kommen solche in Betracht, in denen die Polyarylenethersulfon-Polymere löslich sind, wobei unter "löslich" verstanden wird, dass sich bei Raumtemperatur (20°C) mindestens 10 Gew.-%, vorzugsweise mindestens 20 Gew.-%, insbesondere mindestens 25 Gew.-% des Polyarylenethersulfon-Polymers bezogen auf das Gesamtgewicht der Lösung im aprotischen polaren Lösungsmittel lösen.Thus, in step (i), a solution of the polyarylene ether sulfone polymer and optionally the hydrophilic polymer in an aprotic polar solvent is provided. Suitable aprotic polar solvents are those in which the polyarylene ether sulfone polymers are soluble, "soluble" meaning that at room temperature (20 ° C.) at least 10% by weight, preferably at least 20% by weight, in particular at least 25% by weight of the polyarylene ether-sulfone polymer based on the total weight of the solution in the aprotic polar solvent.
Vorzugsweise wird die in Schritt (i) erhaltene Lösung vor der Durchführung von Schritt (ii) entgast. Der Fachmann wählt übliche, allgemein bekannte Verfahren zur Entgasung von Flüssigkeiten.Preferably, the solution obtained in step (i) is degassed prior to performing step (ii). The person skilled in the art chooses customary, generally known methods for degassing liquids.
Bevorzugte aprotische polare Lösungsmittel zur Bereitstellung der Lösung in Schritt (i) sind N-Methylpyrrolidon, Dimethylacetamid, Dimethylsulfoxid, Dimethylformamid und Sulfolan (Tetrahydrothiophen-1,1-dioxid). Besonders bevorzugt sind N-Methylpyrrolidon, Dimethylacetamid, Dimethylsulfoxid, und Dimethylformamid.Preferred aprotic polar solvents for providing the solution in step (i) are N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, dimethylformamide and sulfolane (tetrahydrothiophene-1,1-dioxide). Particularly preferred are N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, and dimethylformamide.
Die Herstellung der Lösung in Schritt (i) kann in üblichen Behältnissen erfolgen, insbesondere in solchen, welche eine Rührvorrichtung und bevorzugt eine Vorrichtung zur Temperaturkontrolle umfassen. Das Herstellen der Lösung gemäß Schritt (i) des erfindungsgemäßen Verfahrens erfolgt bevorzugt unter Rühren. Das Auflösen des erfindungsgemäßen Polyarylenethersulfon-Polymers und gegebenenfalls des hydrophilen Polymers kann nacheinander oder gleichzeitig erfolgen.The preparation of the solution in step (i) can be carried out in conventional containers, in particular in those which comprise a stirring device and preferably a device for temperature control. The solution according to step (i) of the process according to the invention is preferably carried out with stirring. The dissolution of the polyarylene ether sulfone polymer according to the invention and optionally of the hydrophilic polymer can be carried out successively or simultaneously.
Die Dauer des Schrittes (i) kann in einem weiten Bereich variieren. Vorzugsweise beträgt die Dauer des Schrittes (i) von 10 Minuten bis 48 Stunden, insbesondere von 10 Minuten bis 12 Stunden, besonders bevorzugt von 15 Minuten bis 6 Stunden. Der Fachmann wählt die Dauer des Schrittes (i), so dass eine homogene Lösung des erfindungsgemäßen Polyarylenethersulfon-Polymers und gegebenenfalls des hydrophilen Polymers im aprotischen polaren Lösungsmittel erhalten wird.The duration of step (i) can vary within a wide range. The duration of step (i) is preferably from 10 minutes to 48 hours, in particular from 10 minutes to 12 hours, particularly preferably from 15 minutes to 6 hours. The skilled person chooses the duration of step (i), so that a homogeneous solution of the Polyarylene ether sulfone polymer according to the invention and optionally the hydrophilic polymer is obtained in the aprotic polar solvent.
Vorzugsweise erfolgt die Durchführung des Schrittes (i) bei erhöhter Temperatur, insbesondere von 20°C bis 120°C, vorzugsweise von 40°C bis 100°C. Der Fachmann wählt die Temperatur insbesondere in Abhängigkeit vom aprotischen polaren Lösungsmittel.Preferably, the implementation of step (i) at elevated temperature, in particular from 20 ° C to 120 ° C, preferably from 40 ° C to 100 ° C. The skilled person selects the temperature in particular as a function of the aprotic polar solvent.
Die bevorzugte Konzentration des erfindungsgemäßen Polyarylenethersulfon-Polymers und gegebenenfalls des hydrophilen Polymers im aprotischen polaren Lösungsmittel hängt insbesondere von der Natur des Schrittes (ii) ab.
Vorzugsweise enthält die in Schritt (i) bereitgestellte Lösung von 5 bis 40 Gew.-%, insbesondere von 10 bis 30 Gew.-%, des erfindungsgemäßen Polyarylenethersulfon-Polymers, bezogen auf das Gesamtgewicht der Lösung.The preferred concentration of the polyarylene ether sulfone polymer according to the invention and optionally of the hydrophilic polymer in the aprotic polar solvent depends in particular on the nature of step (ii).
Preferably, the solution provided in step (i) contains from 5 to 40% by weight, in particular from 10 to 30% by weight, of the polyarylene ether sulfone polymer according to the invention, based on the total weight of the solution.
Für den Fall das die in Schritt (i) bereitgestellte Lösung zusätzlich ein hydrophiles Polymer enthält beträgt die Summe des erfindungsgemäßen Polyarylenethersulfon-Polymers und des hydrophilen Polymers 5 bis 40 Gew.-%, insbesondere von 10 bis 30 Gew.-%, bezogen auf das Gesamtgewicht der Lösung.In the case where the solution provided in step (i) additionally contains a hydrophilic polymer, the sum of the polyarylene ether sulfone polymer of the present invention and the hydrophilic polymer is 5 to 40% by weight, more preferably 10 to 30% by weight, based on Total weight of the solution.
In diesem Fall liegt das Gew.-%-Verhältnis von erfindungsgemäßem Polyarylenethersulfon-Polymer zu hydrophilem Polymer in der Lösung in Schritt (i) im Allgemeinen im Bereich von 98 zu 2 bis 50 zu 50.In this case, the weight% ratio of polyarylene ether sulfone polymer to hydrophilic polymer in the solution in step (i) is generally in the range of 98 to 2 to 50 to 50.
Anschließend erfolgt gemäß Schritt (ii) die Trennung des erfindungsgemäßen Polyarylenethersulfon-Polymers bzw. der Mischung aus dem erfindungsgemäßen Polyarylenethersulfon-Polymer und dem hydrophilen Polymer vom aprotischen polaren Lösungsmittel unter Ausbildung einer Membran.Subsequently, according to step (ii), the separation of the polyarylene ether sulfone polymer according to the invention or the mixture of the polyarylene ether sulfone polymer according to the invention and the hydrophilic polymer from the aprotic polar solvent takes place to form a membrane.
Grundsätzlich kann die Form der Membran variieren, wobei die Membran insbesondere in Form einer Folie, in Form einer Schicht auf einem Träger oder in Form einer Faser vorliegt. Im Rahmen einer bevorzugten Ausführungsform ist die Membran gemäß der vorliegenden Erfindung eine Hohlfasermembran, insbesondere eine Hohlfasermembran für Dialyseanwendungen.In principle, the shape of the membrane may vary, the membrane being present in particular in the form of a film, in the form of a layer on a carrier or in the form of a fiber. Within the scope of a preferred embodiment, the membrane according to the present invention is a hollow-fiber membrane, in particular a hollow-fiber membrane for dialysis applications.
Sofern mittels des erfindungsgemäßen Verfahrens Hohlfasermembranen hergestellt werden, wird Schritt (ii) vorzugsweise mittels Nassverspinnen durchgeführt, das heißt, die in Schritt (i) hergestellte Lösung wird in Schritt (ii) zu einer Faser nassversponnen. Sofern in Schritt (ii) ein Nassspinnverfahren zur Anwendung kommt, ist ein Trockendüsen-Nassspinnverfahren besonders bevorzugt.If hollow-fiber membranes are produced by means of the process according to the invention, step (ii) is preferably carried out by wet spinning, that is to say the solution prepared in step (i) is wet-spun into a fiber in step (ii). If a wet spinning process is used in step (ii), a dry jet wet spinning process is particularly preferred.
Unter Trockendüsen-Nassspinnverfahren wird im Rahmen der vorliegenden Erfindung verstanden, dass Schritt (ii) folgende Schritte umfasst:
- (ii-a) Extrudieren der Lösung aus Schritt (i) aus einer Düse in eine gasförmige Atmosphäre, insbesondere Luft, optional in Gegenwart einer Kernflüssigkeit und
- (ii-b) Einführen der in Schritt (ii-a) extrudierten Faser in mindestens ein Koagulationsbad umfassend jeweils ein Behälter und eine Koagulationsflüssigkeit.
- (ii-a) extruding the solution from step (i) from a nozzle into a gaseous atmosphere, in particular air, optionally in the presence of a core liquid and
- (ii-b) introducing the fiber extruded in step (ii-a) into at least one coagulating bath comprising a container and a coagulating liquid, respectively.
Gegenstand der vorliegenden Erfindung ist somit auch ein Verfahren, bei dem Schritt (ii) folgende Schritte umfasst:
- (ii-a) Extrudieren der Lösung aus Schritt (i) aus einer Düse in eine gasförmige Atmosphäre optional in Gegenwart einer Kernflüssigkeit unter Erhalt einer extrudierten Faser und
- (ii-b) Einführen der in Schritt (ii-a) extrudierten Faser in mindestens ein Koagulationsbad umfassend einen Behälter und eine Koagulationsflüssigkeit.
- (ii-a) extruding the solution of step (i) from a nozzle into a gaseous atmosphere optionally in the presence of a core liquid to obtain an extruded fiber and
- (ii-b) introducing the fiber extruded in step (ii-a) into at least one coagulation bath comprising a container and a coagulating liquid.
Dabei kommt üblicherweise eine spezielle Düse mit Kern zum Einsatz, durch den während des Verspinnens eine Kernflüssigkeit gespült wird. Unter Kernflüssigkeit ist im Rahmen der vorliegenden Erfindung eine Flüssigkeit zu verstehen, die im Kern der Spinndüse mit der in Schritt (i) bereitgestellten Lösung in Kontakt kommt. Die Kernflüssigkeit besitzt koagulierende Eigenschaften und dient der Stabilisierung des Kerns der Hohlfaser während des Nassspinnverfahrens.Usually, a special nozzle with core is used, through which a core liquid is rinsed during spinning. For the purposes of the present invention, core liquid is to be understood as meaning a liquid which comes into contact with the solution provided in step (i) in the core of the spinneret. The core liquid has coagulating properties and serves to stabilize the core of the hollow fiber during the wet spinning process.
Der Abstand zwischen Düse und Koagulationsflüssigkeit im Koagulationsbad wird als Trockenzone bezeichnet und beträgt vorzugsweise von 0,1 bis 100 cm, insbesondere von 0,5 bis 50 cm, vorzugsweise von 1 bis 30 cm.The distance between the nozzle and the coagulation liquid in the coagulation bath is referred to as the drying zone and is preferably from 0.1 to 100 cm, in particular from 0.5 to 50 cm, preferably from 1 to 30 cm.
Die Struktur der Poren in der Hohlfasermembran wird durch die Koagulationsflüssigkeit beeinflusst, in der das erfindungsgemäße Polyarylenethersulfon-Polymer bzw. die Mischung aus dem erfindungsgemäßen Polyarylenethersulfon-Polymer und dem hydrophilen Polymer vorzugsweise nicht oder nicht vollständig löslich ist. Die Koagulationsflüssigkeit verursacht ein zumindest partielles Ausfällen des zu verspinnenden Polymers im Koagulationsbad in Form einer Faser.The structure of the pores in the hollow fiber membrane is influenced by the coagulation liquid in which the polyarylene ether sulfone polymer according to the invention or the mixture of the inventive polyarylene ether sulfone polymer and the hydrophilic polymer is preferably not or not completely soluble. The coagulation liquid causes at least partial precipitation of the polymer to be spun in the coagulation bath in the form of a fiber.
Als Koagulationsflüssigkeiten und als Kernflüssigkeiten kommen vorzugsweise Flüssigkeiten in Betracht, welche mit dem aprotischen polaren Lösungsmittel der in Schritt (i) bereitgestellten Lösung vollständig mischbar sind unter der Voraussetzung, dass das erfindungsgemäße Polyarylenethersulfon-Polymer bzw. die Mischung aus dem erfindungsgemäßen Polyarylenethersulfon-Polymer und dem hydrophilen Polymer, in der Koagulationsflüssigkeit nicht oder teilweise nicht löslich ist.Suitable coagulation liquids and core liquids are preferably liquids which are completely miscible with the aprotic polar solvent of the solution provided in step (i) provided that the inventive polyarylene ether sulfone polymer or the mixture of the inventive polyarylene ether sulfone polymer and the hydrophilic polymer in which coagulation liquid is not or partially insoluble.
Der Fachmann wählt Kern- und Koagulationsflüssigkeit in Bezug auf das aprotische polare Lösungsmittel der in Schritt (i) bereitgestellten Lösung so, dass die Flüssigkeiten einerseits mischbar sind und andererseits im Anschluss an das Verspinnen abtrennbar, das heißt in reiner Form wieder gewinnbar, sind, wobei eine destillative Abtrennung bevorzugt ist.The person skilled in the art selects nucleation and coagulation liquid with respect to the aprotic polar solvent of the solution provided in step (i) such that the liquids are, on the one hand, miscible and, on the other hand, separable, ie recoverable in pure form, after spinning a distillative separation is preferred.
Vorzugsweise wird als Kernflüssigkeit eine Mischung aus dem aprotischen polaren Lösungsmittel und deionisiertem Wasser eingesetzt, insbesondere N-Methylpyrrolidon und Wasser. Das Mischungsverhältnis (Gewichtsverhältnis) von NMP zu Wasser beträgt vorzugsweise von 15:1 bis 1:15, besonders bevorzugt von 5:1 bis 1:5, insbesondere 2:1 bis 1:2.The core liquid used is preferably a mixture of the aprotic polar solvent and deionized water, in particular N-methylpyrrolidone and water. The mixing ratio (weight ratio) of NMP to water is preferably from 15: 1 to 1:15, more preferably from 5: 1 to 1: 5, especially from 2: 1 to 1: 2.
Als Koagulationsflüssigkeit wird vorzugsweise mindestens ein aliphatischer Alkohol oder Wasser oder ein Gemisch aus den beiden vorgenannten Verbindungen eingesetzt. Besonders bevorzugt wird im Rahmen des Schrittes (ii-b) des erfindungsgemäßen Verfahrens in einem ersten Koagulationsbad ein aliphatischer Alkohol, insbesondere Ethanol oder Isopropanol, gegebenenfalls im Gemisch mit Wasser, und in einem zweiten Koagulationsbad Wasser eingesetzt.The coagulation liquid used is preferably at least one aliphatic alcohol or water or a mixture of the two abovementioned compounds. Within the scope of step (ii-b) of the process according to the invention, particular preference is given to using in a first coagulation bath an aliphatic alcohol, in particular ethanol or isopropanol, optionally mixed with water, and water in a second coagulation bath.
Vorzugsweise wird das erfindungsgemäße Polyarylenethersulfon-Polymer in dem erfindungsgemäßen Verfahren zur Herstellung einer Membran in wasserfreier Form eingesetzt. Unter "wasserfrei" soll verstanden werden, dass der Wassergehalt in der in Schritt (i) bereitgestellten Lösung weniger als 5 Gew.-%, vorzugsweise weniger als 2 Gew.-%, insbesondere weniger als 1 Gew.-% beträgt, bezogen auf das Gesamtgewicht der Lösung.The polyarylene ether sulfone polymer according to the invention is preferably used in the process according to the invention for producing a membrane in anhydrous form. By "anhydrous" is meant that the water content in the solution provided in step (i) is less than 5% by weight, preferably less than 2% by weight, in particular less than 1% by weight, based on the Total weight of the solution.
Zur Trocknung des erfindungsgemäßen Polyarylenethersulfon-Polymers kommen dem Fachmann bekannte Verfahren in Betracht, insbesondere die Anwendung von erhöhter Temperatur und/oder Vakuum.For drying the polyarylene ether sulfone polymer according to the invention, processes known to those skilled in the art are possible, in particular the use of elevated temperature and / or vacuum.
Nach der Durchführung der Schritte (i) und (ii) des erfindungsgemäßen Verfahrens erfolgt optional (iii) die Aufbereitung der Membran, wobei unter Aufbereitung ein oder mehrere Schritte ausgewählt aus Reinigung, Auswaschen und Nachvernetzung durchgeführt werden.After carrying out steps (i) and (ii) of the process according to the invention, optionally, (iii) the preparation of the membrane is carried out, wherein one or more steps selected from purification, washing out and postcrosslinking are carried out under treatment.
Gegenstand der vorliegenden Erfindung ist auch die Membran, die nach dem erfindungsgemäßen Verfahren erhältlich ist.The present invention also relates to the membrane obtainable by the process according to the invention.
Die erfindungsgemäßen Membranen, insbesondere die erfindungsgemäßen Hohlfasermembranen, weisen eine hohe mechanische Belastbarkeit im Dauergebrauch auf. Sie besitzen eine niedrige Ausschlussgrenze bei der Ultrafiltration, insbesondere der Dialyse.The membranes according to the invention, in particular the hollow-fiber membranes according to the invention, have a high mechanical load-bearing capacity Continuous use. They have a low exclusion limit in ultrafiltration, in particular dialysis.
Gegenstand der vorliegenden Erfindung ist auch eine Membran enthaltend das erfindungsgemäße Polyarylenethersulfon-Polymer. Weiterhin Gegenstand der vorliegenenden Erfindung ist eine Membran, erhältlich nach dem erfindungsgemäßen Verfahren zur Herstellung einer Membran.The present invention also relates to a membrane comprising the polyarylene ether sulfone polymer according to the invention. Further subject of the present invention is a membrane, obtainable by the process according to the invention for producing a membrane.
Gegenstand der vorliegenden Erfindung ist somit auch eine Hohlfaser für die Dialyse, die nach dem erfindungsgemäßen Verfahren erhältlich ist.The present invention thus also relates to a hollow fiber for dialysis, which is obtainable by the process according to the invention.
Gegenstand der vorliegenden Erfindung ist weiterhin die Verwendung des nach dem erfindungsgemäßen Verfahren erhältlichen Polyarylenethersulfon-Polymers zur Herstellung von Membranen.The present invention furthermore relates to the use of the polyarylene ether sulfone polymer obtainable by the process according to the invention for the production of membranes.
Die vorliegende Erfindung wird durch die nachfolgenden Ausführungsbeispiele näher erläutert, ohne sie jedoch hierauf zu beschränken.
Mn, Mw und Q wurden wie vorstehend beschrieben bestimmt.M n , M w and Q were determined as described above.
Die Viskositätszahl VZ wurde nach DIN ISO 1628-1 in einer 1-Gew.-%igen NMP-Lösung bei 25°C gemessen.The viscosity number VZ was measured according to DIN ISO 1628-1 in a 1% strength by weight NMP solution at 25.degree.
Die Isolierung der Polyarylethersulfon-Polymere erfolgt durch Zertropfung einer NMP-Lösung der Polymere in VE-Wasser bei Raumtemperatur (20°C). Die Fallhöhe beträgt 0,5 m. Der Durchsatz beträgt ca. 2,5 I pro Stunde. Die erhaltenen Perlen werden anschließend bei 85 °C für zwanzig Stunden mit Wasser extrahiert (Wasserdurchsatz 160 l/h). Danach werden die Perlen bei einer Temperatur unterhalb der Glastemperatur Tg auf eine Restfeuchte von weniger als 0,1 Gew.-% getrocknet.The isolation of the polyarylethersulfone polymers is carried out by grafting a NMP solution of the polymers in demineralized water at room temperature (20 ° C). The drop height is 0.5 m. The throughput is approx. 2.5 l per hour. The resulting beads are then extracted at 85 ° C for twenty hours with water (water flow 160 l / h). Thereafter, the beads are dried at a temperature below the glass transition temperature T g to a residual moisture content of less than 0.1 wt .-%.
Die volumengemittelte Partikelgröße (D[4,3]) des verwendeten Kaliumkarbonats bzw. Natriumkarbonats wurde mit einem Mastersizer 2000 der Firma Malvern an einer Suspension der Partikel in Chlorbenzol/Sulfolan (60/40) bestimmt.The volume-average particle size (D [4,3]) of the potassium carbonate or sodium carbonate used was determined using a Mastersizer 2000 from Malvern on a suspension of the particles in chlorobenzene / sulfolane (60/40).
Die Molekulargewichtsverteilung der Polyarylethersulfon-Polymere wurde durch GPC-Messung in DMAc bestimmt. Die Molekulargewichte der Polyarylethersulfon-Polymere wurden auch durch Viskositätsmessungen (1 gew.-%-ige Lösung in NMP) charakterisiert.The molecular weight distribution of the polyarylethersulfone polymers was determined by GPC measurement in DMAc. The molecular weights of the polyarylethersulfone polymers were also characterized by viscosity measurements (1 wt.% Solution in NMP).
Der Anteil an cyclischem Dimer wurde mittels HPLC mit THF als flüssiger Phase und PLGEL® Säulen bestimmt.The proportion of cyclic dimer was determined by HPLC with THF as the liquid phase and PLGEL ® columns.
Die vorteilhaften Eigenschaften der erfindungsgemäßen Polyarylethersulfon-Polymere für Membrananwendungen wurden anhand folgender Versuche demonstriert.The advantageous properties of the polyarylethersulfone polymers according to the invention for membrane applications were demonstrated by the following experiments.
Die Lösungen zur Herstellung der Hohlfasermembran wurden wie folgt hergestellt: Zuerst wurde das Polyarylethersulfon-Polymer in NMP gelöst. Anschließend wurde Polyvinylpyrrolidon (PVP, Mw=360.000 g/mol, Tg=176°C, Fa. Merck) zu dieser Lösung hinzugefügt, bis die Zusammensetzung 16/10/74 Gew.-% (Polyarylethersulfon-Polymere /PVP/NMP) erreicht wurde. Diese Lösung wurde anschließend 48 h bei Raumtemperatur gerührt. Vor dem Verspinnen wurden die Lösungen 1 Tag entgast.The solutions for producing the hollow fiber membrane were prepared as follows: First, the polyarylethersulfone polymer was dissolved in NMP. Subsequently, polyvinylpyrrolidone (PVP, M w = 360,000 g / mol, T g = 176 ° C, Merck) was added to this solution until the composition 16/10/74 wt .-% (polyarylethersulfone polymers / PVP / NMP ) has been achieved. This solution was then stirred for 48 h at room temperature. Before spinning, the solutions were degassed for one day.
Die Herstellung der Hohlfasermembranen erfolgte im Trockendüsen-Nassspinnverfahren gemäß der Publikation
Die Zusammensetzung der Kernflüssigkeit war dabei 55:45 Gewichtsteile NMP:deionisiertes Wasser. Die Distanz zwischen der Spinndüse und dem Fällbad betrug 20 cm. Zur Fällung wurde ein 2-stufiger Fällprozess mit Isopropanol als erste Koagulationsflüssigkeit im ersten Fällbad und Wasser als zweite Koagulationsflüssigkeit im zweiten Fällbad verwendet. Die Abzugsgeschwindigkeit der Fasern war gleich der Spinngeschwindigkeit (8,6 cm/s). Anschließend wurden die Fasern 3 Tage in Wasser gelagert. Vor der Zug-Dehnungsmessung werden die Fasern aus dem Wasser entnommen, äußerlich anhaftendes Wasser wird entfernt, danach werden die Proben 48 Stunden bei 23°C und 50% relativer Luftfeuchtigkeit gelagert. Danach werden die Fasern auf eine Länge von 150 mm geschnitten und in einer Zwick/Roell Zug-Dehnungsapparatur Z010 mit einer Dehnrate von 20 mm/min bis zum Bruch gezogen.The composition of the core liquid was 55:45 parts by weight NMP: deionized water. The distance between the spinneret and the precipitation bath was 20 cm. For precipitation, a 2-stage precipitation process with isopropanol was used as first coagulation liquid in the first precipitation bath and water as second coagulation liquid in the second precipitation bath. The take-off speed of the fibers was equal to the spinning speed (8.6 cm / s). Subsequently, the fibers were stored in water for 3 days. Before the tensile strain measurement, the fibers are removed from the water, externally adhering water is removed, then the samples are stored for 48 hours at 23 ° C and 50% relative humidity. Thereafter, the fibers are cut to a length of 150 mm and pulled in a Zwick / Roell tensile-stretching apparatus Z010 at a strain rate of 20 mm / min to break.
Die Ergebnisse der Prüfungen sind in Tabellen 1 aufgeführt.The results of the tests are shown in Tables 1.
In einen 4L-Reaktor mit Innenthermometer, Gaseinleitungsrohr, Rückflusskühler mit Wasserabscheider wurden 430,62 g DCDPS, 342,08 g Bisphenol A und 222,86 g Kaliumkarbonat einer volumengemittelten Partikelgröße von 32,4 µm unter Stickstoffatmosphäre in 641 ml NMP suspendiert. Innerhalb 1 h wird der Ansatz auf 190°C erhitzt. Als Reaktionsdauer wird die Verweilzeit bei 190°C betrachtet. Das Reaktionswasser wird abdestilliert und der Füllstand durch Zufügen von NMP während der Reaktion konstant gehalten. Nach 8 h Reaktionszeit wird die Reaktion durch Verdünnung mit kaltem NMP (1609 ml) abgebrochen, anschließend wird bei 140°C für 45 Minuten Methylchlorid (10 l/h) in den Ansatz eingeleitet (45 Minuten). Danach wird Stickstoff eingeleitet (20 l/h) und der Ansatz abgekühlt. Das entstandene Kaliumchlorid wird abfiltriert.Into a 4 L reactor with internal thermometer, gas inlet tube, reflux condenser with water separator 430.62 g of DCDPS, 342.08 g of bisphenol A and 222.86 g of potassium carbonate of a volume-average particle size of 32.4 .mu.m were suspended in 641 ml of NMP under a nitrogen atmosphere. Within 1 h, the batch is heated to 190 ° C. The reaction time is considered to be the residence time at 190.degree. The water of reaction is distilled off and the level is kept constant by adding NMP during the reaction. After a reaction time of 8 hours, the reaction is stopped by dilution with cold NMP (1609 ml), then methyl chloride (10 l / h) is introduced into the reaction at 140 ° C. for 45 minutes (45 minutes). Thereafter, nitrogen is introduced (20 l / h) and cooled the approach. The resulting potassium chloride is filtered off.
In einen 4L-Reaktor mit Innenthermometer, Gaseinleitungsrohr, Rückflusskühler mit Wasserabscheider wurden 430,62 g DCDPS, 342,08 g Bisphenol A und 222,86 g Kaliumkarbonat einer volumengemittelten Partikelgröße von 22,4 µm unter Stickstoffatmosphäre in 641 ml NMP suspendiert. Innerhalb 1 h wird der Ansatz auf 190°C erhitzt. Als Reaktionsdauer wird die Verweilzeit bei 190°C betrachtet. Das Reaktionswasser wird abdestilliert und der Füllstand durch Zufügen von NMP während der Reaktion konstant gehalten. Nach 6,5 h Reaktionszeit wird die Reaktion durch Verdünnung mit kaltem NMP (1609 ml) abgebrochen, anschließend wird bei 140°C für 45 Minuten Methylchlorid (10 l/h) in den Ansatz eingeleitet (45 Minuten). Danach wird Stickstoff eingeleitet (20 l/h) und der Ansatz abgekühlt. Das entstandene Kaliumchlorid wird abfiltriert.Into a 4L reactor with internal thermometer, gas inlet tube, reflux condenser with water separator, 430.62 g of DCDPS, 342.08 g of bisphenol A and 222.86 g of potassium carbonate with a volume-average particle size of 22.4 μm were suspended under nitrogen in 641 ml of NMP. Within 1 h, the batch is heated to 190 ° C. The reaction time is considered to be the residence time at 190.degree. The water of reaction is distilled off and the level is kept constant by adding NMP during the reaction. After a reaction time of 6.5 hours, the reaction is stopped by dilution with cold NMP (1609 ml), then methyl chloride (10 l / h) is introduced into the reaction at 140 ° C. for 45 minutes (45 minutes). Thereafter, nitrogen is introduced (20 l / h) and cooled the approach. The resulting potassium chloride is filtered off.
In einen 4L-Reaktor mit Innenthermometer, Gaseinleitungsrohr, Rückflusskühler mit Wasserabscheider wurden 430,62 g DCDPS, 342,08 g Bisphenol A und 222,86 g Kaliumkarbonat einer volumengemittelten Partikelgröße von 12,4 µm unter Stickstoffatmosphäre in 641 ml NMP suspendiert. Innerhalb 1 h wird der Ansatz auf 190°C erhitzt. Als Reaktionsdauer wird die Verweilzeit bei 190°C betrachtet. Das Reaktionswasser wird abdestilliert und der Füllstand durch Zufügen von NMP während der Reaktion konstant gehalten. Nach 5 h Reaktionszeit wird die Reaktion durch Verdünnung mit kaltem NMP (1609 ml) abgebrochen, anschließend wird bei 140°C für 45 Minuten Methylchlorid (10 l/h) in den Ansatz eingeleitet (45 Minuten). Danach wird Stickstoff eingeleitet (20 l/h) und der Ansatz abgekühlt. Das entstandene Kaliumchlorid wird abfiltriert.Into a 4L reactor with internal thermometer, gas inlet tube, reflux condenser with water separator 430.62 g of DCDPS, 342.08 g of bisphenol A and 222.86 g of potassium carbonate of a volume-average particle size of 12.4 microns were suspended in 641 ml of NMP under a nitrogen atmosphere. Within 1 h, the batch is heated to 190 ° C. The reaction time is considered to be the residence time at 190.degree. The water of reaction is distilled off and the level is kept constant by adding NMP during the reaction. After a reaction time of 5 hours, the reaction is stopped by dilution with cold NMP (1609 ml), then methyl chloride (10 l / h) is introduced into the reaction at 140 ° C. for 45 minutes (45 minutes). Thereafter, nitrogen is introduced (20 l / h) and cooled the approach. The resulting potassium chloride is filtered off.
In einen 4L-Reaktor mit Innenthermometer, Gaseinleitungsrohr, Rückflusskühler mit Wasserabscheider wurden 430,62 g DCDPS, 342,08 g Bisphenol A und 170,91 g Natriumkarbonat einer Partikelgröße von 23,2 µm unter Stickstoffatmosphäre in 641 ml NMP suspendiert. Innerhalb 1 h wird der Ansatz auf 190°C erhitzt. Als Reaktionsdauer wird die Verweilzeit bei 190°C betrachtet. Das Reaktionswasser wird abdestilliert und der Füllstand durch Zufügen von NMP während der Reaktion konstant gehalten. Nach 9 h Reaktionszeit wird die Reaktion durch Verdünnung mit kaltem NMP (1609 ml) abgebrochen, anschließend wird bei 140°C für 45 Minuten Methylchlorid (10 l/h) in den Ansatz eingeleitet (45 Minuten). Danach wird Stickstoff eingeleitet (20 l/h) und der Ansatz abgekühlt. Das entstandene Natriumchlorid wird abfiltriert.Into a 4L reactor with internal thermometer, gas inlet tube, reflux condenser with water separator, 430.62 g of DCDPS, 342.08 g of bisphenol A and 170.91 g of sodium carbonate having a particle size of 23.2 μm were suspended in 641 ml of NMP under a nitrogen atmosphere. Within 1 h, the batch is heated to 190 ° C. The reaction time is considered to be the residence time at 190.degree. The water of reaction is distilled off and the level is kept constant by adding NMP during the reaction. After a reaction time of 9 hours, the reaction is stopped by dilution with cold NMP (1609 ml), then methyl chloride (10 l / h) is introduced into the reaction at 140 ° C. for 45 minutes (45 minutes). Thereafter, nitrogen is introduced (20 l / h) and cooled the approach. The resulting sodium chloride is filtered off.
In einen 4L-Reaktor mit Innenthermometer, Gaseinleitungsrohr, Rückflusskühler mit Wasserabscheider wurden 430,62 g DCDPS, 342,08 g Bisphenol A und 170,91 g Natriumkarbonat einer Partikelgröße von 11,9 µm unter Stickstoffatmosphäre in 641 ml NMP suspendiert. Innerhalb 1 h wird der Ansatz auf 190°C erhitzt. Als Reaktionsdauer wird die Verweilzeit bei 190°C betrachtet. Das Reaktionswasser wird abdestilliert und der Füllstand durch Zufügen von NMP während der Reaktion konstant gehalten. Nach 9 h Reaktionszeit wird die Reaktion durch Verdünnung mit kaltem NMP (1609 ml) abgebrochen, anschließend wird bei 140°C für 45 Minuten Methylchlorid (10 l/h) in den Ansatz eingeleitet (45 Minuten). Danach wird Stickstoff eingeleitet (20 l/h) und der Ansatz abgekühlt. Das entstandene Natriumchlorid wird abfiltriert.Into a 4L reactor with internal thermometer, gas inlet tube, reflux condenser with water separator 430.62 g of DCDPS, 342.08 g of bisphenol A and 170.91 g of sodium carbonate with a particle size of 11.9 microns were suspended under nitrogen atmosphere in 641 ml of NMP. Within 1 h, the batch is heated to 190 ° C. The reaction time is considered to be the residence time at 190.degree. The water of reaction is distilled off and the level is kept constant by adding NMP during the reaction. After a reaction time of 9 hours, the reaction is stopped by dilution with cold NMP (1609 ml), then methyl chloride (10 l / h) is introduced into the reaction at 140 ° C. for 45 minutes (45 minutes). Thereafter, nitrogen is introduced (20 l / h) and cooled the approach. The resulting sodium chloride is filtered off.
In einen 4L-Reaktor mit Innenthermometer, Gaseinleitungsrohr, Rückflusskühler mit Wasserabscheider wurden 574,16 g DCDPS, 379,87 g Dihydroxybiphenyl und 286,09 g Kaliumkarbonat einer Partikelgröße von 23,2 µm unter Stickstoffatmosphäre in 2100 ml NMP suspendiert. Innerhalb 1 h wird der Ansatz auf 190°C erhitzt. Als Reaktionsdauer wird die Verweilzeit bei 190°C betrachtet. Das Reaktionswasser wird abdestilliert und der Füllstand durch Zufügen von NMP während der Reaktion konstant gehalten. Nach 6 h Reaktionszeit wird die Reaktion durch Verdünnung mit kaltem NMP (900 ml) abgebrochen, anschließend wird bei 140°C für 45 Minuten Methylchlorid (10 l/h) in den Ansatz eingeleitet (45 Minuten). Danach wird Stickstoff eingeleitet (20 l/h) und der Ansatz abgekühlt. Das entstandene Kaliumchlorid wird abfiltriert.
Die erfindungsgemäßen Polyarylenethersulfon-Polymere weisen bei kürzerer Reaktionszeit vergleichbare Viskositätszahlen (VZ), aber engere Molekulargewichtsverteilung auf. Aus diesen Polyarylenethersulfon-Polymere hergestellte Hohlfasermembranen weisen überraschenderweise bessere mechanische Eigenschaften auf. Die Versuche V4 und V5 zeigen, dass bei der Verwendung von Natriumkarbonat kein ausreichender Molekulargewichtsaufbau erreicht wird, daher wurden keine weiteren Analysen durchgeführt. Beispiel V6 zeigt, dass PPSU eine breitere Molekulargewichtsverteilung aufweist. Unter den für V1, 2 und 3 gewählten Versuchsbedingungen konnte aus dem Polyarylenethersulfon-Polymer gemäß Beispiel V6 keine Hohlfasermembran hergestellt werden.The polyarylene ether sulfone polymers according to the invention have comparable viscosity numbers (VZ) but a narrower molecular weight distribution for a shorter reaction time. Surprisingly, hollow fiber membranes produced from these polyarylene ether sulfone polymers have better mechanical properties. Experiments V4 and V5 show that the use of sodium carbonate does not achieve sufficient molecular weight buildup, therefore no further analyzes were performed. Example V6 shows that PPSU has a broader molecular weight distribution. Under the experimental conditions chosen for V1, 2 and 3, no hollow fiber membrane could be produced from the polyarylene ether sulfone polymer according to Example V6.
Claims (15)
die Komponente (B1) mindestens 50 Gew.-% 4,4'-Dihydroxydiphenylsulfon enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG),
die Komponente (C) im Wesentlichen aus Kaliumcarbonat mit einer volumengemittelten Partikelgröße von < 25 µm besteht und die Komponente (D) im Wesentlichen aus N-Methylpyrrolidon besteht.A process according to any one of claims 1 to 3, characterized in that component (A1) contains at least 50% by weight of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1) in the reaction mixture (R G ),
component (B1) contains at least 50% by weight of 4,4'-dihydroxydiphenylsulfone, based on the total weight of component (B1) in the reaction mixture (R G ),
the component (C) consists essentially of potassium carbonate having a volume-average particle size of <25 microns and the component (D) consists essentially of N-methylpyrrolidone.
die Komponente (B1) mindestens 50 Gew.-% Bisphenol A enthält, bezogen auf das Gesamtgewicht der Komponente (B1) im Reaktionsgemisch (RG),
die Komponente (C) im Wesentlichen aus Kaliumcarbonat mit einer volumengemittelten Partikelgröße von < 25 µm besteht und
die Komponente (D) im Wesentlichen aus N-Methylpyrrolidon besteht.A process according to any one of claims 1 to 3, characterized in that component (A1) contains at least 50% by weight of 4,4'-dichlorodiphenyl sulfone, based on the total weight of component (A1) in the reaction mixture (R G ),
Component (B1) contains at least 50% by weight of bisphenol A, based on the total weight of component (B1) in the reaction mixture (R G ),
the component (C) consists essentially of potassium carbonate having a volume-average particle size of <25 microns, and
the component (D) consists essentially of N-methylpyrrolidone.
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